WO2020009039A1

WO2020009039A1 - Organic el element and display device, image pickup device, communication equipment, illumination device, lamp fitting, and mobile body using said organic el element

Info

Publication number: WO2020009039A1
Application number: PCT/JP2019/025944
Authority: WO
Inventors: 広和宮下; ▲高▼谷　格; 希之伊藤; 萌恵 ▲高▼比良; 智奈山口; 塩原　悟; 友和小竹; 春奈飯田; 山田　直樹; 鎌谷　淳
Original assignee: キヤノン株式会社
Priority date: 2018-07-05
Filing date: 2019-06-28
Publication date: 2020-01-09

Abstract

This organic EL element is at least provided with an anode 2, a first light-emitting layer 4a, an intermediate layer 5, a second light-emitting layer 4b, and a cathode 7 in this order, the intermediate layer 5 being disposed adjacent to the first light-emitting layer 4a and the second light-emitting layer 4b, wherein the first light-emitting layer 4a and the second light-emitting layer 4b are capable of trapping electrons, and the intermediate layer 5 is composed of a hydrocarbon material that has a high S₁ level and a HOMO level not higher than that of a host material in the first light-emitting layer 4a.

Description

Organic EL element and display device, imaging device, communication device, lighting device, lamp, moving body using the same

The present invention relates to an organic EL element that emits light by passing a current through an organic EL (electroluminescence) layer including a light emitting layer, which is sandwiched between a pair of electrodes, and various devices using the organic EL element.

Recently, research and development of full-color light-emitting arrays using organic EL elements have been actively pursued. When a full-color light-emitting array is manufactured, there are a method in which a light-emitting layer is separately applied to each pixel (element) and a method in which a color filter is applied to each pixel using an organic EL element in which the light-emitting layer emits white light. As for the organic EL element, two or more kinds of light emitting materials are often used.

Patent Document 1 discloses an organic EL device in which a plurality of light-emitting layers are stacked, a charge barrier layer is provided between two light-emitting layers, and light emission efficiency is improved.

Patent Document 2 discloses an organic material in which three light-emitting layers are stacked, and an intermediate layer made of the same material as the host of the light-emitting layer is provided between the light-emitting layers to cause the three light-emitting layers to emit light and improve the light emission balance. An EL element is disclosed.

WO 2010/134350 pamphlet JP 2011-151011 A

However, the organic EL device disclosed in Patent Document 1 did not have sufficient durability characteristics. In the organic EL device of Patent Document 1, the energy level (HOMO level) of the HOMO (highest occupied orbit) of the charge barrier layer (intermediate layer) provided between the two light emitting layers is higher than that of the host of the surrounding light emitting layer. large. That is, in other words, the element configuration is such that the HOMO level of the intermediate layer is closer to the vacuum level than the HOMO level of the adjacent light emitting layer. Therefore, since holes are accumulated in the intermediate layer sandwiched between the two light emitting layers, quenching of excitons due to accumulated charges and material deterioration due to accumulation of charges may occur.

(4) The organic EL device disclosed in Patent Document 2 did not have a sufficient red, green, and blue light emission balance. In the organic EL device of Patent Document 2, of the two intermediate layers (first intermediate layer and second intermediate layer) provided between the three light emitting layers, the first intermediate layer material adjacent to the red light emitting layer is a red light emitting layer. Is formed of the same material as that of the host forming the device. Therefore, energy transfer from the green or blue light-emitting layer located on the opposite side of the red light-emitting layer with respect to the first intermediate layer easily occurs to the red light-emitting layer via the first intermediate layer, and light emission accompanying the energy transfer is performed. A change in balance or a decrease in luminous efficiency may occur.

Furthermore, it is considered that depending on the material structure, the intermediate layer also causes a reduction in the efficiency of the element and a deterioration of the element.

The present invention has been made in order to solve the above problems, and provides an organic EL device having improved durability characteristics and excellent light emission balance, and various devices using the organic EL device.

The first of the present invention comprises at least an anode, a first light-emitting layer, an intermediate layer, a second light-emitting layer, and a cathode in this order, wherein the intermediate layer has the first light-emitting layer and the second light-emitting layer. An organic EL element adjacent to the layer,
The first light-emitting layer contains a first host and a first dopant,
The second light-emitting layer contains a second host and a second dopant,
The intermediate layer contains an aromatic hydrocarbon compound,
The following relationship (a) holds between the first host and the first dopant,
The following relationship (b) holds between the second host and the second dopant,
The following relationship (c) is established between the intermediate layer material and the first host.
(A) LUMO (H1)> LUMO (D1)
(B) LUMO (H2)> LUMO (D2)
(C) HOMO (H1) ≧ HOMO (IL)
[In the above (a) to (c), LUMO (H1), LUMO (D1), LUMO (H2), and LUMO (D2) are the first host, the first dopant, the second host, and the second dopant, respectively. HOMO (H1) and HOMO (IL) represent the energy levels of the HOMO of the first host and the intermediate layer material, respectively. A second aspect of the present invention is a display device having a plurality of pixels, wherein the pixels have the organic EL element of the present invention and an active element connected to the organic EL element. I do.

A third aspect of the present invention is a foldable display device having a flexible substrate and a display unit disposed on the flexible substrate, wherein the display unit is the organic EL element of the present invention, And an active element connected to the organic EL element.

A fourth aspect of the present invention is an imaging device including an optical unit having a plurality of lenses, an imaging element that receives light passing through the optical unit, and a display unit that displays an image, wherein the display unit is A display unit that displays an image captured by the imaging element, wherein the display unit includes the organic EL element of the present invention.

第 A fifth aspect of the present invention is a communication device including a display unit and a communication unit, wherein the display unit includes the organic EL element of the present invention.

第 A sixth aspect of the present invention is a lighting device including a light source and a light diffusing unit, wherein the light source includes the organic EL element of the present invention.

第 A seventh aspect of the present invention is a lighting device having a light source, wherein an optical film is provided on a light emitting side of the light source, and the light source has the organic EL element of the present invention.

An eighth aspect of the present invention is a lamp including the organic EL element of the present invention and a protection member for protecting the organic EL element.

A ninth aspect of the present invention is a moving body including a body and a lamp provided on the body, wherein the lamp includes the organic EL element of the present invention.

According to the present invention, it is possible to provide an organic EL device having improved durability characteristics and good light emission balance. Therefore, a display device, an imaging device, a communication device, a lighting device, a lamp, and a moving object which are excellent in required characteristics are provided by using the organic EL element.

FIG. 1 is a schematic sectional view schematically showing the configuration of an embodiment of the organic EL device of the present invention. FIG. 1 is a schematic sectional view schematically showing the configuration of an embodiment of the organic EL device of the present invention. FIG. 1 is a schematic sectional view schematically showing the configuration of an embodiment of the organic EL device of the present invention. FIG. 2 is an energy diagram schematically showing the energy level of each layer constituting the organic EL device of the present invention. FIG. 3 is a schematic cross-sectional view of an example of a display device using the organic EL element of the present invention. FIG. 4 is an exploded perspective view schematically showing the configuration of another example of the display device using the organic EL element of the present invention. FIG. 5 is a schematic rear view illustrating an example of an imaging device using the organic EL element of the present invention. FIG. 6 is a perspective view schematically illustrating an example of a portable communication device using the organic EL element of the present invention. FIG. 7 is a schematic front view showing another example of the display device using the organic EL element of the present invention. FIG. 7 is a schematic front view showing another example of the display device using the organic EL element of the present invention. FIG. 8 is an exploded perspective view illustrating a configuration of an example of a lighting device using the organic EL element of the present invention. FIG. 9 is a schematic view illustrating an example of an automobile using the organic EL element of the present invention for a lamp.

The organic EL (electroluminescence) element of the present invention includes at least an anode, a first light-emitting layer, an intermediate layer, a second light-emitting layer, and a cathode in this order. It is arranged between the two light emitting layers. The first light-emitting layer on the anode side contains a first host and a first dopant, the second light-emitting layer on the cathode side has a second host and a second dopant, and the intermediate layer is a constituent material. (Hereinafter, referred to as “intermediate layer material”).

Here, in each light-emitting layer, the energy level of the LUMO (lowest unoccupied orbit) of the host (hereinafter, referred to as “LUMO level”) is larger than the energy level of the LUMO of the dopant (close to the vacuum level). ). Further, the energy level of the HOMO (highest occupied orbit) of the intermediate layer material (hereinafter, referred to as “HOMO level”) is smaller (farther from the vacuum level) than the HOMO level of the first host material. Has features. Hereinafter, the present invention will be described in more detail with reference to FIG.

FIG. 1 is a diagram schematically showing the configuration of the embodiment of the organic EL device of the present invention, and is a cross-sectional view in the laminating direction.

In the organic EL device shown in FIG. 1A, an anode 2, a hole transport layer 3, a first light emitting layer 4a, an intermediate layer 5, a second light emitting layer 4b, a third light emitting layer 4c, and an electron transport layer 6 are formed on a substrate 1. And the cathode 7 are stacked in this order. The first light emitting layer 4a, the second light emitting layer 4b, and the third light emitting layer 4c respectively contain dopants of different emission colors.

The organic EL device shown in FIG. 1B includes an anode 2, a hole transport layer 3, a third light emitting layer 4c, a first light emitting layer 4a, an intermediate layer 5, a second light emitting layer 4b, and an electron transport layer 6 on a substrate 1. And the cathode 7 are stacked in this order. The first light emitting layer 4a, the second light emitting layer 4b, and the third light emitting layer 4c respectively contain dopants of different emission colors.

1C, an anode 2, a hole transport layer 3, a first light emitting layer 4a, an intermediate layer 5, a second light emitting layer 4b, an electron transport layer 6, and a cathode 7 are formed on a substrate 1 in this order. It is laminated. The first light emitting layer 4a contains two kinds of dopants of different emission colors, and the second light emitting layer 4b contains a dopant of a different emission color from the dopant contained in the first light emitting layer 4a.

The

light emitting layers

4a, 4b, 4c shown in FIGS. 1A to 1C are all fluorescent light emitting layers. The

light emitting layers

4a, 4b, 4c may be light emitting layers emitting any colors. For example, light emission may be the same color, or different colors may be emitted. Further, the light emitting layer may emit white light as a whole. In the case of emitting light of different colors, white light may be emitted from the red, green, and blue light emitting layers.

In the present invention, the light emitting layer means a layer having a light emitting function among organic compound layers provided between the anode 2 and the cathode 7. The host included in the light-emitting layer refers to a material which is a main component among materials included in each light-emitting layer. More specifically, the host refers to a material included in the light emitting layer and having a content of more than 50% by mass in the light emitting layer. On the other hand, the dopant is a material that is not a main component among the materials included in the light emitting layer. More specifically, the dopant refers to a material having a content of less than 50% by mass in the light emitting layer among the materials included in the light emitting layer. The concentration of the dopant in the light emitting layer is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 10% by mass or less in order to suppress concentration quenching.

In addition, in each of the devices shown in FIG. 1, a hole injection layer may be provided between the anode 2 and the hole transport layer 3, and an electron blocking layer may be provided between the hole transport layer 3 and the light emitting layer. Further, a hole blocking layer may be provided between the light emitting layer and the electron transport layer 6, and an electron injection layer may be provided between the electron transport layer 6 and the cathode 7. These hole injection layer, electron block layer, hole block layer, and electron injection layer are appropriately used in the present invention as needed.

FIG. 2 is an energy diagram schematically showing the energy levels around the light emitting layer constituting the organic EL device of the present invention.

As shown in FIG. 2, in the present invention, the following relationship (a) is established between the first host and the first dopant contained in the first light emitting layer 4a.
(A) LUMO (H1)> LUMO (D1)

において In (a) above, LUMO (H1) and LUMO (D1) represent the LUMO levels of the first host and the first dopant, respectively.

On the other hand, the following relationship (b) is established between the second host and the second dopant contained in the second light emitting layer 4b.
(B) LUMO (H2)> LUMO (D2)

において In (b) above, LUMO (H2) and LUMO (D2) represent the LUMO levels of the second host and the second dopant, respectively.

Further, the following relationship (c) is established between the intermediate layer material forming the intermediate layer 5 and the first host included in the first light emitting layer 4a.
(C) HOMO (H1) ≧ HOMO (IL)

において In (c) above, HOMO (H1) and HOMO (IL) represent the HOMO levels of the first host and the intermediate layer material, respectively.

Ｈ Note that the HOMO level and the LUMO level are based on the vacuum level, and take negative values in the case of ordinary molecules. Therefore, when comparing the HOMO level and the LUMO level, those having a small value (large absolute value) are far from the vacuum level, and those having a large value (small absolute value) are the vacuum level. Get closer.

In the present invention, the HOMO level and the LUMO level use numerical values obtained by a molecular orbital calculation method. The molecular orbital calculation method used was a density functional theory (DFT), which is widely used at present. The functional was B3LYP and the basis function was 6-31G ^* . In addition, the molecular orbital calculation method uses Gaussian 09 (Gaussian 09, Revision C.01, MJ Frisch, GW Trucks, HB Schlegel, GE Scuseria, MA) which is currently widely used. Robb, JR Cheeseman, G. Scalmani, V. Barone, B. Mennucci, GA A. Petersson, H. Nakatsuji, M. Caricato, X. Li, HP Hratchian, A. F. Izmaylov. J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, JA Montgomery, Jr., JE Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, KN Kudin, V. N. Starovov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, JC Burant, SS Iyengar, J. Tomasi, M. Regis, N. Regis. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomberts, R. E. Stratmann, O. Yazyev, A. J. Austi , R. Cami, C. Pomerli, JW Ochterski, RL Martin, K. Morokuma, VG Zakrzewski, GA Voth, P. Salvador, J. J. Dannenberg, S. Daprich. , AD Daniels, O. Farkas, JB Foresman, JV Ortiz, J. Cioslowski, and DJ J. Fox, Gaussian, Inc., Wallingford CT, 2010.).

In the examples described below, in order to verify the accuracy of the calculated values, the calculated values obtained by the molecular orbital calculation method were compared with the actually measured values.

As shown in FIGS. 1A to 1C and 2, the organic EL device of the present invention has at least two fluorescent

light emitting layers

4a and 4b, and an intermediate layer 5 is provided between the light emitting

layers

4a and 4b. It has an element configuration. And since it has the following characteristics, it becomes an organic EL element which is excellent in durability characteristics and light emission balance.
(1) The two light emitting

layers

4a and 4b sandwiching the intermediate layer 5 have an electron trapping property.
(2) The HOMO level of the intermediate layer material is equal to or lower than the HOMO level of the first host on the anode 2 side. (3) The intermediate layer material is a hydrocarbon.
(4) The energy level of the lowest excited singlet (S ₁ ) of the intermediate layer material (hereinafter, referred to as “S ₁ level”) is high.

特徴 These features are described below.

(1) The two light emitting

layers

4a and 4b sandwiching the intermediate layer 5 have an electron trapping property.
Charges (holes, electrons) in the light-emitting layer move in the light-emitting layer while moving back and forth between the levels of the host and the dopant. In other words, the charge in the light emitting layer moves in the light emitting layer while being repeatedly trapped by the host or the dopant or detrapped by the host or the dopant. At this time, the larger the difference between the HOMO level or the LUMO level between the host and the dopant, the lower the charge mobility.

More specifically, when the LUMO level of the dopant is smaller than the LUMO level of the host, an electron trapping property is generated in the light emitting layer, and the smaller the LUMO level of the dopant, the better the electron trapping property. When the HOMO level of the dopant is higher than the HOMO level of the host, hole-trapping properties are generated in the light-emitting layer.

Here, in the present invention, the above-mentioned relations (a) and (b) hold. That is, in FIG. 1, the two light emitting

layers

4a and 4b sandwiching the intermediate layer 5 become light emitting layers having an electron trapping property, and the electron mobility of each light emitting

layer

4a and 4b is reduced. By doing so, the recombination region is localized on the electron transport layer 6 side.

In general, an amine compound used as a material for a hole transport layer has an unshared electron pair (lawn pair), and thus is stable against being in a radical cation state that has released an electron, but is a radical that has received an electron. It is a compound that is unstable in the anionic state. That is, when the electrons injected from the cathode 7 reach the hole transport layer 3, the electrons and the amine compound forming the hole transport layer 3 interact with each other to cause deterioration of the material. It is thought to happen. In the present invention, since the two light emitting

layers

4a and 4b sandwiching the intermediate layer 5 have an electron trapping property, the recombination region is unevenly distributed on the electron transport layer 6 side. As a result, deterioration of the hole transport layer 3 due to electrons can be prevented, and an organic EL device having excellent durability characteristics can be obtained.

(2) The HOMO level of the intermediate layer material is equal to or lower than the HOMO level of the first host on the anode 2 side.
In the organic EL device in which a plurality of light emitting layers are stacked, when the recombination region is unevenly distributed on the electron transport layer 6 side as in the above (1), only the

light emitting layers

4b and 4c on the electron transport layer 6 side emit light, It is considered that it is difficult to obtain white light emission.

Here, it has been found that the relationship (c) is required in the present invention. As a result, a hole barrier is generated between the first light emitting layer 4a and the intermediate layer 5, so that the number of holes existing in the first light emitting layer 4a can be increased, and the recombination region is formed on the hole transport layer 3 side. Can also be expanded. As a result, it is possible to cause each of the stacked

light emitting layers

4a and 4b to emit light, thereby obtaining white light emission.

(4) The electrons that have reached the first light emitting layer 4a are trapped by the electron trapping property of the first light emitting layer 4a. Then, recombination with holes existing at the interface between the first light emitting layer 4a and the intermediate layer 5 occurs quickly, so that electrons reaching the hole transport layer 3 can be restricted. As a result, the deterioration of the hole transport layer 3 due to electrons as described above is not promoted.

In the case of the intermediate layer 5 that does not satisfy the relationship (c) above, that is, when the HOMO level of the intermediate layer 5 is higher than the HOMO level of the first host, there is no hole barrier, so that hole transport is not performed. Is difficult to restrict, and the recombination region is limited to the intermediate layer 5 and the second light emitting layer 4b. As a result, an excessive exciton is confined in the intermediate layer 5 and the second light emitting layer 4b, which may cause quench and material deterioration.

(3) The intermediate layer material is a hydrocarbon.
The present inventors have found that the intermediate layer material constituting the intermediate layer 5 is preferably a hydrocarbon. In the present invention, the intermediate layer 5 is responsible for transferring charges between the first light emitting layer 4a and the second light emitting layer 4b and adjusting the carrier balance. In particular, in order to control holes flowing into the second light emitting layer 4b, it is required that holes be accumulated at the interface between the first light emitting layer 4a and the intermediate layer 5. That is, it is necessary that the intermediate layer has a molecular structure that can withstand excessive generation of radical cations, and a hydrocarbon having high chemical stability is preferable as the intermediate layer material. In general, a compound having a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom has an unshared electron pair and is therefore active in donating and accepting electrons, that is, redox. For this reason, chemical stability is low because unpaired electrons generated through the transfer of electrons may cause material degradation due to interaction such as causing a disproportionation reaction. On the other hand, hydrocarbons do not have lone pairs of electrons and have high chemical stability, and thus are preferred as intermediate layer materials.

(4) _{S 1} level of the intermediate layer material is high.
The intermediate layer material has a role of not only adjusting the carrier balance but also suppressing the energy transfer between the first light emitting layer 4a and the second light emitting layer 4b. Since the organic EL device of the present invention is a light-emitting device using a fluorescent light-emitting dopant, the intermediate layer 5 is preferably a compound having a sufficiently high S ₁ level. Specifically, the S ₁ level is preferably 2.58 eV or more. In order to suppress energy transfer at a wavelength of 430 nm to 480 nm, which is a blue region, the S ₁ level is preferably 2.58 eV or more, more preferably 2.88 eV or more, and desirably 3.00 eV or more. It is. A material having a high S ₁ level is an aromatic hydrocarbon compound. Specifically, the molecular structure is formed by bonding one or more aromatic hydrocarbons selected from benzene, naphthalene, fluorene, benzofluorene, phenanthrene, anthracene, chrysene, triphenylene, pyrene, fluoranthene, and benzofluoranthene. Compound. Incidentally, S ₁ level here is a numerical value calculated by molecular orbital calculations described above.

When the intermediate layer 5 suppresses energy transfer of a wavelength in the green region, that is, 500 nm or more and 570 nm or less, the S ₁ level is preferably 2.18 eV or more, more preferably 2.48 eV or more, Desirably, it is 2.50 eV or more. When suppressing energy transfer at a wavelength of 580 nm to 680 nm, which is a red region, the S ₁ level is preferably 2.14 eV or more, more preferably 1.82 eV or more, and preferably 1 or more. 80 eV or more.

Furthermore, an acene compound in which a benzene ring is linearly condensed is easily oxidized because of a substitution position having a high electron density in the central benzene ring, and has low chemical stability among aromatic hydrocarbons. Accordingly, benzene, naphthalene, benzofluorene, fluorene, phenanthrene, chrysene, triphenylene, pyrene, fluoranthene, and benzofluoranthene, excluding anthracene, which is an acene compound, are particularly preferable.

Further, in the case of being composed only of benzene and naphthalene, the band gap becomes large, and an unnecessary excessive barrier is formed between the first light emitting layer 4a and the second light emitting layer 4b as an electron and hole injection barrier. Would. This may make it difficult to adjust the carrier balance and may cause material degradation due to local electric field concentration due to charge accumulation. Therefore, the S ₁ level of the intermediate layer material is preferably 3.3 eV or less, more preferably 3.2 eV or less. Specifically, as the intermediate layer material, a compound having at least one of fluorene, benzofluorene, phenanthrene, chrysene, triphenylene, pyrene, fluoranthene, and benzofluoranthene as a part of its molecular structure is desirable. In addition, from the viewpoint of not generating an excessive hole barrier, the difference between the HOMO level of the first light emitting layer and the host material is preferably 0.5 eV or less in molecular orbital calculation. More preferably, it is within 0.3 eV.

In the case of an organic EL element in which a plurality of light-emitting layers are stacked, unlike a single-color organic EL element having a single-layer light-emitting layer, good white can be realized unless the relationship between the plurality of light-emitting layers is considered. Can not. In particular, when the above characteristics (1) to (4) are satisfied, that is, the two light emitting

layers

4a and 4b sandwiching the intermediate layer 5 have an electron trapping property, and the HOMO level of the intermediate layer material is or less HOMO level of the first host side, the interlayer material is a hydrocarbon, if S ₁ level is high, it is possible to obtain an organic EL device having excellent light emission balance and durability.

Further, it is preferable that the element configuration satisfy the following conditions because the effects of the above features (1) to (4) are enhanced.
(5) When the third light emitting layer 4c is provided, the third light emitting layer 4c also has an electron trapping property. When the third light emitting layer 4c is not provided, the third dopant (fluorescent light emission) is included in the first light emitting layer 4a. It is in a relationship between the first host and the electron trap.
(6) The first light emitting layer 4a has a hole trapping property.
(7) The HOMO level of the second dopant in the second light emitting layer 4b is smaller than the HOMO level of the second host.
(8) The electron trapping property of each of the

light emitting layers

4a, 4b, 4c is larger than the hole trapping property.
(9) The second light emitting layer 4b is a blue light emitting layer.
(10) Each host material is a hydrocarbon.
(11) Each dopant has a fluoranthene skeleton.

Hereinafter, these will be described.

(5) When the third light-emitting layer 4c is provided, the third light-emitting layer 4c also has an electron trapping property. When the third light-emitting layer 4c is not provided, the third dopant is contained in the first light-emitting layer 4a. There is a relationship between the host and the electron trap.
The

light emitting layers

4a, 4b, and 4c shown in FIG. 1 are each composed of at least a host and a dopant. That is, the first light emitting layer 4a contains a first host and a first dopant, and the second light emitting layer 4b contains a second host and a second dopant. As shown in FIGS. 1A and 1B, when the third light emitting layer 4c is provided, the third light emitting layer 4c contains a third host and a third dopant. As shown in FIG. 1C, when the third light emitting layer 4c is not provided, the first light emitting layer 4a contains the third dopant in addition to the first dopant.

1A, a third light emitting layer 4c adjacent to the second light emitting layer 4b is provided between the second light emitting layer 4b and the cathode 7, or as shown in FIG. When a third light emitting layer 4c adjacent to the first light emitting layer 4a is provided between the third host and the second dopant, it is preferable that the following relationship (d) be established between the third host and the third dopant.
(D) LUMO (H3)> LUMO (D3)

において In (d) above, LUMO (H3) and LUMO (D3) represent the LUMO levels of the third host and the third dopant, respectively. By having the relationship (d), the third light emitting layer 4c has an electron trapping property.

In the case of FIG. 1A, by further providing the electron trapping light emitting layer on the electron transport layer 6 side, the recombination region is unevenly distributed on the electron transport layer 6 side, and the durability characteristics can be improved. Further, as shown in FIG. 1B, by further providing the electron-trapping light-emitting layer on the hole transport layer 3 side, electrons reaching the hole transport layer 3 can be suppressed, and the durability characteristics can be improved. .

In addition, as shown in FIG. 1C, when the third light emitting layer 4c is not provided, the first light emitting layer 4a further has a third dopant, and the following (e) between the first host and the third dopant. Is preferably established.
(E) LUMO (H1)> LUMO (D3)

において In (e) above, LUMO (D3) represents the LUMO level of the third dopant. By having the relationship (e), the electron trapping property of the first light emitting layer 4a can be enhanced, the electrons reaching the hole transport layer 3 can be suppressed, and the durability characteristics can be improved. .

(6) The first light emitting layer 4a has a hole trapping property.
Furthermore, in the first light emitting layer 4a, it is preferable that the following relationship (f) be established between the first host and the first dopant.
(F) HOMO (H1) <HOMO (D1)

において In (f) above, HOMO (H1) and HOMO (D1) represent the HOMO levels of the first host and the first dopant, respectively. By having the relationship (f), the first light emitting layer 4a has a hole trapping property, so that the balance of the amount of holes flowing into the second light emitting layer 4b, which has been adjusted only by the injection barrier of the intermediate layer 5, can be improved. It is easier to adjust. As a result, the recombination region is also extended to the hole transport layer 3 side, and it becomes easy to realize well-balanced white light emission. That is, by adjusting the amount of holes transported to the second light emitting layer 4b by the hole trapping property of the first light emitting layer 4a and the hole injection barrier by the intermediate layer 5, it is possible to realize a carrier balance that easily emits white light. it can.

(7) The HOMO level of the second dopant in the second light emitting layer 4b is smaller than the HOMO level of the second host.
Furthermore, in the second light emitting layer 4b, it is preferable that the following relationship (g) be established between the second host and the second dopant.
(G) HOMO (H2)> HOMO (D2)

において In (g) above, HOMO (H2) and HOMO (D2) represent the HOMO levels of the second host and the second dopant, respectively. By having the relationship (g), the hole trapping property in the second light emitting layer 4b can be suppressed. As a result, the effect of distributing the recombination region to the electron transport layer 6 side can be enhanced. For example, according to the relationship (g), as shown in FIG. 1A, in the case of a laminated structure having the third light emitting layer 4c on the electron transporting 6 side, the hole trapping property of the second light emitting layer 4b is low, so that the third light emitting layer Enhances hole transport to 4c. Therefore, the effect of distributing the recombination region to the electron transport layer 6 side can be enhanced. When the relationship (g) is satisfied, the electron trapping property of the second light emitting layer 4b can be relatively improved.

(8) The electron trapping property of each of the

light emitting layers

4a, 4b, 4c is higher than the hole trapping property.
In addition to the fact that the hole transport layer 3 is prevented from being deteriorated, the fact that the light emitting layer having the electron trapping property is effective in improving the durability characteristics will be described.

Science, 283, 1900 (1999) suggests that one of the causes of degradation of tris (8-quinolinolato) aluminum (Alq3), which is the host of the light-emitting layer, is the instability of radical cations generated by hole conduction. Have been. In order to suppress such deterioration due to radical cations in the light emitting layer, it is preferable to lower the hole density in the light emitting layer to lower the probability of becoming a radical cation. For that purpose, it is preferable to reduce the hole trapping property, increase the electron trapping property, and increase the electron density in the light emitting layer.

Specifically, using the first light emitting layer 4a of FIG. 2, the following relationship (h) is preferable. (H) LUMO (H1) -LUMO (D1)> HOMO (D1) -HOMO (H1)

(4) With the above relationship (h), the hole trapping property of the first light emitting layer 4a can be reduced, and the electron trapping property can be improved.

Further, when the relationship (g) and the relationship (h) are satisfied, the hole trapping property of the first light emitting layer 4a is further reduced in combination with the relationship (b), and the electron trapping is relatively performed. Can be enhanced. As a result, by increasing the electron density of each light emitting layer as a whole sandwiching the intermediate layer 5, the recombination probability can be increased, and as a result, the hole density can be reduced.

(9) The second light emitting layer 4b is a blue light emitting layer.
1A, the first dopant contained in the first light emitting layer 4a preferably emits red light, and the second dopant contained in the second light emitting layer 4b and the third dopant contained in the third light emitting layer 4c It is preferable that one of them emits green light and the other emits blue light. By including a red light-emitting dopant having a narrow band gap in the first light-emitting layer 4a, the first light-emitting layer 4a can easily exhibit the above-described hole trapping property and also easily have a hole barrier with the intermediate layer 5. Further, in the present invention, the recombination region is localized on the electron transport layer 6 side. Therefore, the lamination structure in which the excitation energy generated by the blue light emitting dopant and the green light emitting dopant having a wide band gap can transfer energy to the red light emitting dopant on the hole transport layer 3 side has better white light emission with better balance. This is because it is easy to realize durability characteristics.

It is particularly preferable that the second light emitting layer 4b is a blue light emitting layer. This is because by using a blue light emitting dopant having a wide band gap, it is easy to satisfy the above relationships (b) and (g), and the hole trapping property of the second light emitting layer 4b can be reduced.

1B, the third dopant contained in the third light emitting layer 4c is red light emission, the first dopant contained in the first light emitting layer 4a is green light emission, and the second dopant contained in the second light emitting layer 4b. Preferably emits blue light. By including a red light-emitting dopant having a narrow band gap in the third light-emitting layer 4c, the third light-emitting layer 4c becomes a light-emitting layer having a high electron trapping property, and can suppress electrons reaching the hole transport layer 3, thereby improving durability. This is because the characteristics are improved. Further, in the present invention, the recombination region is localized on the electron transport layer 6 side. Therefore, the lamination structure in which the excitation energy generated by the blue light-emitting dopant having a wide band gap can transfer energy to the red light-emitting dopant and the green light-emitting dopant on the hole transport layer 3 side has better white light emission with better balance. This is because it is easy to realize durability characteristics.

1C, the first dopant and the third dopant contained in the first light emitting layer 4a are preferably a red light emitting dopant and a green light emitting dopant, and the second dopant contained in the second light emitting layer 4b. Is preferably a blue light emitting dopant. By including a red light-emitting dopant having a narrow band gap in the first light-emitting layer 4a, the first light-emitting layer 4a becomes a light-emitting layer having a high electron trapping property, and can suppress electrons reaching the hole transport layer 3; This is because the characteristics are improved. Further, in the present invention, the recombination region is localized on the electron transport layer 6 side. Therefore, the stacked structure in which the excitation energy of the blue light-emitting dopant having a wide band gap can be transferred to the red light-emitting dopant and the green light-emitting dopant on the hole transport layer 3 side has a well-balanced white light emission and excellent durability. Easy to realize characteristics.

{Circle around (4)} When a red light emitting dopant and a green light emitting dopant having different band gaps are mixed in the first light emitting layer 4a, energy transfer to a red light emitting dopant having a narrower band gap tends to occur. Therefore, it is preferable that the doping concentration of the red light emitting dopant be lower than the doping concentration of the green light emitting dopant. Preferably, the concentration of the red light-emitting dopant is preferably 1/5 or less, more preferably 1/10 or less, of the green light-emitting dopant concentration by mass ratio. Thereby, the emission intensity balance of the red and green dopants can be adjusted.

As a result, it is preferable for the organic EL device of the present invention that the second light emitting layer 4b is a blue light emitting layer in the laminated structure of FIGS. 1A to 1C.

In the present specification, the term “blue light-emitting dopant” refers to a light-emitting material having a peak wavelength of an emission spectrum of 430 nm to 480 nm. In addition, a green light emitting dopant refers to a light emitting material having a peak wavelength of an emission spectrum of 500 nm to 570 nm, and a red light emitting dopant light refers to a light emitting material having a peak wavelength of a light emission spectrum of 580 nm to 680 nm.

(10) Each host material is a hydrocarbon.
In the present invention, the compound used as the host of the light emitting layers 4a to 4c is not particularly limited, but a compound having no bond with low bond stability in the molecular structure is more preferable. When a compound having a bond with low bond stability in a molecular structure, that is, a compound having an unstable bond with small binding energy is included as a host in a light-emitting layer included in an organic EL device, drive deterioration of the compound during driving of the device is reduced. Easy to happen. As a result, the durability of the organic EL element is likely to be adversely affected.

Taking the [4,4′-bis (carbazol-9-yl) biphenyl] (CBP) shown below as an example, a bond having low bond stability is a bond connecting a carbazole ring and a phenylene group (nitrogen-carbon bond). ). The comparison of the calculated values of the binding energies of the exemplary compound EM1 of the CBP and the host and the exemplary compound HT7 of the hole injection / transport material is shown below. The calculation was performed using b3-lyp / def2-SV (P).

From the above results, it is preferable that the host of the light emitting layers 4a to 4c of the organic EL device of the present invention be a hydrocarbon having a high bond stability composed of a carbon-carbon bond. On the other hand, when the host is a hydrocarbon, the LUMO level of the host is small. Therefore, in order to form a light-emitting layer having high electron trapping properties, the LUMO level of the dopant is required to be small.

(11) Each dopant has a fluoranthene skeleton.
In the present invention, the compound used as the dopant contained in the light emitting layers 4a to 4c is not particularly limited, but from the viewpoint of the electron trapping property described in the above (10), it has a fluoranthene skeleton having an electron-withdrawing structure. Is preferred. By having a fluoranthene skeleton, the LUMO level is reduced, the difference in LUMO level from the host material is increased, and the electron trapping property can be improved. Further, it is preferable to have no electron-donating substituted amino group since the LUMO level becomes small and the electron trapping property becomes high. Further, from the viewpoint of bond stability, it is preferable that the compound does not have a substituted amino group that becomes a nitrogen-carbon bond.

As described above, when the host is a hydrocarbon and the dopant is a compound having a fluoranthene skeleton and having no substituted amino group, the light-emitting layers 4a to 4c having high electron trapping properties can be formed. Further, in this case, the stability of the material itself for forming the light emitting layers 4a to 4c is high, so that an organic EL element exhibiting excellent durability characteristics can be obtained.

Here, the fluoranthene skeleton will be described. The fluoranthene skeleton refers to fluoranthene and a condensed polycyclic compound in which an aromatic hydrocarbon is further condensed with fluoranthene. Specifically, it refers to a condensed polycyclic compound as shown in FF1 to FF30 below.

ドーパント Among the fluoranthene-based compounds of FF1 to FF30, a dopant having a structure in which two or more fluoranthenes are condensed is preferable from the viewpoint of improving the electron withdrawing property and improving the electron trapping property. Specifically, a dopant having a skeleton of FF7 to FF13, FF16 to FF20, and FF23 to FF30 can be suitably used in the present invention.

As described above, when the above conditions (5) to (10) are satisfied, that is, the electron trapping property by the third dopant is increased, the hole trapping property of each light emitting layer is low, and the second light emitting layer 4b is a blue light emitting layer. In addition, when the host is a hydrocarbon and the dopant has a fluoranthene skeleton, an organic EL device having particularly excellent durability characteristics and emission balance can be obtained.

具体 Specific examples of the host used in the present invention are shown below. However, these compounds are only specific examples, and the present invention is not limited thereto.

ホスト Among the hosts of EM1 to EM31, hydrocarbons EM1 to EM26 are preferable from the viewpoint of the above-mentioned bond stability. By using these compounds as a host, an organic EL device having excellent durability can be obtained.

において In the present invention, in addition to the specific examples described above, a carbazole derivative, a dibenzofuran derivative, a dibenzothiophene derivative, an organic aluminum complex such as tris (8-quinolinolate) aluminum, an organic beryllium complex, and the like are used as the host.

青 Examples of the blue light emitting dopant used in the present invention include the following. However, the present invention is not limited to this.

のうち Of the blue light emitting dopants of BD1 to BD31, it is preferable not to have a substituted amino group having a high electron donating property from the viewpoint of electron trapping properties. Further, by having a cyano group having a high electron-withdrawing property, the LUMO level of the dopant can be reduced and the electron-trapping property of the light-emitting layer can be improved, which is preferable.

ドープ The doping concentration of the blue light emitting dopant is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass. If the concentration is too low, the probability of electron trapping decreases, and the probability of recombination decreases, leading to a decrease in blue emission intensity. Conversely, if the concentration is too high, concentration quenching occurs, which is not desirable.

緑 As the green light emitting dopant used in the present invention, for example, the following can be used. However, the present invention is not limited to this.

のうち Among the green light-emitting dopants GD1 to GD32, compounds having no substituted amino group having a high electron-donating property are preferable from the viewpoint of electron trapping properties.

ドープ The doping concentration of the green light emitting dopant is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass. If the concentration is too low, the probability of electron trapping decreases and the probability of recombination decreases, leading to a decrease in green light emission intensity. Conversely, if the concentration is too high, concentration quenching occurs, which is not desirable.

赤 As the red light emitting dopant used in the present invention, for example, the following can be used. However, the present invention is not limited to this.

のうち Among the red light-emitting dopants of RD1 to RD23, hydrocarbons are preferable from the viewpoint of bond stability.

ドープ The doping concentration of the red light emitting dopant is preferably 0.1 to 5% by mass, more preferably 0.1 to 0.5% by mass. If the concentration is too low, the probability of electron trapping decreases, and the probability of recombination decreases, leading to a decrease in the emission intensity of red light. Conversely, if the concentration is too high, concentration quenching occurs, which is not desirable.

In the present invention, in addition to the above-described blue light emitting dopant, green light emitting dopant, and red light emitting dopant, fused ring compounds (for example, fluorene derivatives, naphthalene derivatives, pyrene derivatives, perylene derivatives, tetracene derivatives, anthracene derivatives, rubrene, etc.), quinacridone Derivatives, coumarin derivatives, stilbene derivatives, organoaluminum complexes such as tris (8-quinolinolato) aluminum, iridium complexes, platinum complexes, rhenium complexes, copper complexes, europium complexes, ruthenium complexes, and poly (phenylenevinylene) derivatives, poly (fluorene) ) Derivatives and polymer derivatives such as poly (phenylene) derivatives can also be used.

具体 Specific examples of the intermediate layer material used in the present invention are shown below. However, these compounds are only specific examples, and the present invention is not limited thereto.

The organic EL device of the present invention is an organic electric field device having a pair of electrodes and an organic compound layer (organic EL layer) disposed between the pair of electrodes. The light emitting device has a laminated structure of a light emitting layer / intermediate layer / second light emitting layer. In the present invention, a hole transport layer may be provided between the anode and the first light emitting layer, and further, a configuration having a hole injection layer between the anode and the hole transport layer, or a hole transport layer An electron blocking layer may be provided between the light emitting layer and the first light emitting layer. Further, in the present invention, an electron transporting layer may be provided between the cathode and the second light emitting layer, and further, an electron injection layer may be provided between the cathode and the electron transporting layer. A hole blocking layer may be provided between the first light emitting layer and the second light emitting layer.

In particular, a structure having both a hole transporting layer and an electron blocking layer, and a structure having both an electron transporting layer and a hole blocking layer can confine both hole and electron carriers in the light emitting layer, so that carrier leakage is reduced. And a light-emitting element with high luminous efficiency can be obtained.

In addition, an insulating layer is provided at the interface between the electrode and the organic compound layer, an adhesive layer or an interference layer is provided, the electron transporting layer or the hole transporting layer is composed of two layers having different ionization potentials, and the light emitting layer is made of a different light emitting material. Various layer configurations such as a two-layer configuration can be employed.

有機 The organic EL device of the present invention may be a so-called bottom emission type in which light is extracted from an electrode on the substrate side, a so-called top emission type in which light is extracted from the side opposite to the substrate, or a double-sided extraction structure.

As the hole injecting and transporting material used for the hole transporting layer and the hole injecting layer, a material capable of facilitating the injection of holes from the anode and a material capable of transporting the injected holes to the light emitting layer can be used. Thus, a material having a high hole mobility is preferable. Further, in order to suppress deterioration of film quality such as crystallization in the organic EL device, a material having a high glass transition temperature is preferable. Examples of low-molecular and high-molecular materials having hole injection transport properties include triarylamine derivatives, arylcarbazole derivatives, phenylenediamine derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, poly (vinylcarbazole), poly (thiophene), Other conductive polymers can be used. Further, the above-described hole injecting and transporting material is also suitably used for an electron blocking layer.

具体 Specific examples of the compound used as the hole injecting / transporting material are shown below, but the present invention is not limited thereto.

The electron transporting material used for the electron transporting layer or the electron injecting layer can be arbitrarily selected from those capable of transporting electrons injected from the cathode to the light emitting layer. The selection is made in consideration of the balance with the mobility. Examples of the material having an electron transporting property include oxadiazole derivatives, oxazole derivatives, pyrazine derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, organic aluminum complexes, fused compounds (for example, fluorene derivatives, naphthalene derivatives, Chrysene derivatives, anthracene derivatives, etc.). Furthermore, the above-mentioned electron transporting material is also suitably used for a hole blocking layer.

具体 Specific examples of the compound used as the electron transporting material are shown below, but the present invention is not limited thereto.

Hereinafter, other components will be described with reference to FIG.

As the substrate 1, any material such as quartz, glass, silicon wafer, resin, and metal may be used. Further, a switching element such as a transistor or a wiring may be provided on the substrate 1, and an insulating layer may be provided thereon. As the insulating layer, any material can be used as long as a contact hole can be formed in order to secure conduction between the anode 2 and the wiring, and insulation from an unconnected wiring can be ensured. For example, a resin such as polyimide, silicon oxide, silicon nitride, or the like can be used. In the case of a bottom emission type element, a light transmitting material is used for the substrate 1 and the insulating layer.

As a constituent material of the anode 2, a material having a work function as large as possible is preferable. For example, simple metals such as gold, platinum, silver, copper, nickel, palladium, cobalt, selenium, vanadium, and tungsten, and mixtures containing them, or alloys thereof, tin oxide, zinc oxide, indium oxide, and tin oxide Metal oxides such as indium (ITO) and indium zinc oxide can be used. Also, conductive polymers such as polyaniline, polypyrrole, and polythiophene can be used.

電極 One of these electrode substances may be used alone, or two or more thereof may be used in combination. Further, anode 2 may be composed of a single layer or a plurality of layers.

In the case of a top emission type element, for example, chromium, aluminum, silver, titanium, tungsten, molybdenum, an alloy thereof, or a laminate thereof can be used in order to use the anode 2 as a reflection electrode. In the case of a bottom emission type element, an oxide transparent conductive layer of indium tin oxide (ITO), indium zinc oxide, or the like can be used in order to use the anode 2 as a transparent electrode, but is not limited thereto. Not something.

フォト A photolithography technique can be used to form the electrodes.

On the other hand, the constituent material of the cathode 7 preferably has a small work function. For example, an alkali metal such as lithium, an alkaline earth metal such as calcium, a simple metal such as aluminum, titanium, manganese, silver, lead, and chromium, or a mixture containing these metals may be used. Alternatively, an alloy obtained by combining these metals alone can also be used. For example, magnesium-silver, aluminum-lithium, aluminum-magnesium, silver-copper, zinc-silver and the like can be used. It is also possible to use a metal oxide such as indium tin oxide (ITO). One of these electrode substances may be used alone, or two or more of them may be used in combination. The cathode 7 may have a single-layer structure or a multilayer structure.

In the case of a top emission type device, the cathode 7 may be made transparent using a transparent oxide conductive layer such as ITO. In the case of a bottom emission type device, the cathode 7 may be made of aluminum (Al) or the like. May be used as a reflective electrode. The method for forming the cathode 7 is not particularly limited. However, it is more preferable to use a direct current or alternating current sputtering method because the film has good coverage and the resistance is easily reduced.

封止 After forming the cathode 7, a sealing member (not shown) may be provided. For example, by adhering a glass provided with a hygroscopic agent on the cathode 7, it is possible to suppress the entry of water or the like into the organic compound layer and to suppress the occurrence of display defects. Further, a passivation film such as silicon nitride may be provided on the cathode 7 to suppress entry of water or the like into the organic compound layer. For example, after the cathode 7 is formed, it is transferred to another chamber without breaking the vacuum, and a silicon nitride film having a thickness of 2 μm is formed by a CVD method, so that a sealing film may be formed.

In addition, a color filter may be provided outside the cathode 7 in the case of a top emission type, and outside the substrate 1 in the case of a bottom emission type. The color filter may be separately formed and attached to the organic EL element, or may be directly formed on the organic EL element by using a photolithography technique.

The organic compound layer (a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer) according to the present invention is formed by vacuum evaporation, ionization evaporation, sputtering, It can be formed using a dry process such as plasma. Instead of the dry process, a wet process of forming a layer by a known coating method (for example, spin coating, dipping, casting, LB method, inkjet method, or the like) by dissolving in a suitable solvent can also be used.

すると Here, when the layer is formed by a vacuum deposition method, a solution coating method, or the like, crystallization or the like hardly occurs, and the stability with time is excellent. When the film is formed by a coating method, the film can be formed in combination with an appropriate binder resin.

Examples of the binder resin include, but are not limited to, polyvinyl carbazole resin, polycarbonate resin, polyester resin, ABS resin, acrylic resin, polyimide resin, phenol resin, epoxy resin, silicone resin, and urea resin. . These binder resins may be used alone as a homopolymer or a copolymer, or may be used as a mixture of two or more. If necessary, known additives such as a plasticizer, an antioxidant and an ultraviolet absorber may be used in combination.

有機 The organic EL element of the present invention can be used as a light source of a display device, an imaging device, a communication device, a lighting device, and a lamp.

FIG. 3 is a schematic cross-sectional view showing an example of a display device having an organic light emitting device and an active device connected to the organic light emitting device. The active element may be a transistor or a TFT made of polysilicon, an oxide semiconductor, or the like.

The display device 10 shown in FIG. 3 includes a substrate 11 made of glass or the like and an insulating layer 12 provided on the substrate 11 for protecting the transistor element or the organic compound layer. A transistor element 18 having a gate electrode 13, a gate insulating film 14, a semiconductor layer 15, a drain electrode 16, and a source electrode 17 is provided thereon.

The display device has the organic light emitting element 26 over the transistor element via the interlayer insulating layer 19. The organic light emitting element 26 has an anode 21, an organic compound layer 22 including a light emitting layer, and a cathode 23.

(4) A contact hole 20 is provided in the interlayer insulating layer 19, and the anode 21 and the source electrode 17 constituting the organic light emitting element are connected via the contact hole.

Note that the method of electrical connection between the electrodes (anode and cathode) included in the organic light-emitting element and the electrodes (source and drain electrodes) included in the transistor is not limited to the mode illustrated in FIG. That is, any one of the anode and the cathode may be electrically connected to one of the source electrode and the drain electrode of the transistor element.

表示 Although the organic compound layer 22 is illustrated as one layer in the display device 10 of FIG. 3, the organic compound layer 22 may be a plurality of layers. On the cathode 23, a first protective layer 24 and a second protective layer 25 for suppressing deterioration of the organic light emitting element are provided.

Although the display device 10 of FIG. 3 uses a transistor as a switching element, another element may be used as a switching element instead.

The transistor used in the display device 10 of FIG. 3 is not limited to a transistor using a single crystal silicon wafer, but may be a thin film transistor having an active layer on an insulating surface of a substrate. Examples of the active layer include non-single-crystal silicon such as single-crystal silicon, amorphous silicon, and microcrystalline silicon; and non-single-crystal oxide semiconductors such as indium zinc oxide and indium gallium zinc oxide. Note that a thin film transistor is also called a TFT element.

(3) In the display device 10 of FIG. 3, the light emission luminance of the organic EL element 26 is controlled by the transistor 18. By providing the organic EL element in a plurality of planes, an image can be displayed with each light emission luminance. Note that a TFT is preferably used as the transistor 18. In addition to the transistor, a switching element such as an MIM element or an active matrix driver formed on a substrate such as a Si substrate is preferably used. On the substrate can also be referred to as in the substrate. This is selected depending on the definition. For example, in the case of a definition of about 1 inch and QVGA, it is preferable to provide an organic EL element on a Si substrate. By driving a display device using the organic EL element of the present invention, stable image display with good image quality and long-time display is possible.

FIG. 4 is a schematic diagram illustrating an example of a display device using the display device of FIG. 3 as a display panel. The display device 1000 in FIG. 4 includes a touch panel 1003, a display panel 1005, a frame 1006, a circuit board 1007, and a battery 1008 between an upper cover 1001 and a lower cover 1009. Flexible printed circuits FPCs 1002 and 1004 are connected to the touch panel 1003 and the display panel 1005. Transistors are printed on the circuit board 1007. The battery 1008 need not be provided unless the display device is a portable device, and need not be provided at this position even if the display device is a portable device.

The organic EL element of the present invention may be used in a display unit of an imaging device that includes an optical unit having a plurality of lenses and an image sensor that receives light passing through the optical unit. The imaging device may include a display unit that displays information acquired by the imaging device. Further, the display unit may be a display unit exposed to the outside of the imaging device or a display unit arranged in a viewfinder. The imaging device may be a digital camera or a digital video camera.

FIG. 5 is a schematic diagram illustrating an example of the imaging device. The imaging device 1100 in FIG. 5 includes a viewfinder 1101, a rear display 1102, a housing 1103, and an operation unit 1104. The viewfinder 1101 includes the organic EL element of the present invention, and may display not only a captured image but also environmental information, an imaging instruction, and the like. The environmental information may include the intensity of the external light, the direction of the external light, the moving speed of the subject, the possibility that the subject is blocked by a blocking object, and the like.

タイミング Since the timing suitable for imaging is a short time, it is better to display information as soon as possible. Therefore, the organic EL element of the present invention has a high response speed and is preferable as a display unit of an imaging device. A display device using an organic EL element can be more suitably used in a device requiring a display speed than a liquid crystal display device.

The imaging device 1100 has an optical unit (not shown). The optical unit has a plurality of lenses, and forms an image on an imaging element housed in the housing 1103. The focus of the plurality of lenses can be adjusted by adjusting their relative positions. This operation can be performed automatically.

The display device using the organic EL element of the present invention may include a color filter having red, green, and blue. In the color filters, the red, green, and blue colors may be arranged in a delta arrangement.

The display device using the organic EL element of the present invention may be used for a display unit of a portable terminal. In that case, both the display function and the operation function may be provided. Examples of the mobile terminal include a mobile phone such as a smartphone, a tablet, a head-mounted display, and the like.

FIG. 6 is a schematic view illustrating an example of a portable device using the organic EL element of the present invention for a display portion. The mobile device 1200 includes a display unit 1201, an operation unit 1202, and a housing 1203. The housing 1203 is provided with a circuit, a printed circuit board having the circuit, a battery, and a communication unit. The operation unit 1202 may be a button or a touch panel type reaction unit. The operation unit 1202 may be a biometric recognition unit that recognizes a fingerprint and unlocks the lock. A portable device having a communication unit can also be called a communication device.

FIG. 7 is a schematic diagram illustrating another example of a display device using the organic EL element of the present invention for a display unit. FIG. 7A shows a display device such as a television monitor or a PC monitor. The display device 1300 includes a frame 1301, a display unit 1302, and a base 1303 that supports the frame 1301 and the display unit 1302. The base 1303 is not limited to the form shown in FIG. 7A, and the lower side of the frame 1301 may also serve as the base. In addition, the frame 1301 and the display unit 1302 may be curved, and the radius of curvature thereof may be 5000 mm or more and 6000 mm or less.

FIG. 7B is a schematic view illustrating another example of a display device using the organic EL element of the present invention for a display portion. The display device 1310 in FIG. 7B is configured to be bendable, and is a so-called folderable display device. The display device 1310 includes a first display portion 1311, a second display portion 1312, a housing 1313, and a bending point 1314. The first display portion 1311 and the second display portion 1312 are the organic EL elements of the present invention, and can be separated by a bending point by a single seamless member. The first display unit 1311 and the second display unit 1312 may display different images, respectively, or may display one image with the first and second display units. The housing 1313 is a flexible board.

FIG. 8 is a schematic diagram illustrating an example of a lighting device using the organic EL element of the present invention as a light source. The lighting device 1400 includes a housing 1401, a light source 1402, a circuit board 1403, an optical film 1404, and a light diffusion unit 1405. The optical film 1404 may be a filter for improving the color rendering of the light source 1402, and is disposed on the light emission side of the light source 1402. The light diffusing unit can effectively diffuse light from a light source such as light-up and deliver light to a wide range. If necessary, a cover may be provided on the outermost side.

The lighting device is, for example, a device that illuminates a room. The lighting device may emit white or any other color from blue to red. It may have a dimming circuit for dimming them. The lighting device has a power supply circuit connected to the organic EL element of the present invention for converting an AC voltage to a DC voltage. White has a color temperature of 4200K and daytime has a color temperature of 5000K. The lighting device may have a color filter.

FIG. 9 is a schematic view showing an automobile as an example of a moving body using the organic EL element of the present invention as a lamp. The automobile 1500 has a tail lamp 1501. A tail lamp is an example of a lamp. The tail lamp may be in a form in which the tail lamp is turned on when a brake operation or the like of a vehicle is performed. The tail lamp may have a protection member for protecting the organic EL element. The protective member has a high strength to some extent, and any material may be used as long as it is transparent. However, the protective member is preferably made of polycarbonate or the like. A polycarbonate may be mixed with a furandicarboxylic acid derivative, an acrylonitrile derivative, or the like.

The automobile 1500 may have a fuselage 1503 and a window 1502 attached thereto. The window may be a transparent display as long as it is not a window for confirming the front and rear of the vehicle. The organic EL element of the present invention may be used as the transparent display. In this case, the constituent materials such as the electrodes of the organic EL element are formed of transparent members. The moving object of the present invention may be a ship, a drone, an aircraft, or the like, in addition to the automobile. The lamp included in the moving object may be in a form that emits light to indicate its position.

(Example 1)
<Measurement of HOMO level / LUMO level>
The HOMO level and the LUMO level of the host, the dopant, and the intermediate layer material were measured by the following method. Table 1 shows the results.

A) Measurement of HOMO Level A thin film having a thickness of 30 nm was formed on each aluminum substrate using each material, and the HOMO level of this thin film was measured using AC-3 (manufactured by Riken Keiki Co., Ltd.). The results are shown in Tables 1 and 2.

B) Measurement of LUMO level A thin film having a thickness of 30 nm is formed on each quartz substrate using each material, and the thin film is measured for the material to be measured using a spectrophotometer (“V-560” manufactured by JASCO Corporation). The optical band gap (absorption edge) was determined. The sum of the optical band gap value and the HOMO level described above was taken as the LUMO level. The results are shown in Tables 1 and 2.

Further, Tables 1 and 2 show the calculated values obtained by the molecular orbital calculation method. From the comparison with the actually measured values, it is understood that the HOMO level and the LUMO level have a correlation. Therefore, in this embodiment, the device results are considered using the numerical values of the HOMO level and the LUMO level obtained from the calculated values. In the tables below, the HOMO level and the LUMO level are referred to as “HOMO” and “LUMO”, respectively.

(Example 2)
In the present embodiment, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a first light emitting layer, an intermediate layer, a second light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, An organic EL device having a top emission structure in which cathodes were sequentially formed was manufactured. Specifically, first, a 40 nm-thick Ti film was formed on a glass substrate by a sputtering method, and was patterned using a photolithography technique to form an anode. At this time, the facing area between the anode and the cathode was set to 3 mm ² . Subsequently, the above-described substrate and the material on which the electrodes having been cleaned were formed were attached to a vacuum evaporation apparatus (manufactured by ULVAC, Inc.), and the material was evacuated to 1.33 × 10 ⁻⁴ Pa (1 × 10 ⁻⁶ Torr). Ozone cleaning was performed. Thereafter, each layer was formed with the layer configuration shown in Table 3 below.

(4) After forming the electron injection layer, 500 nm of ITO was formed by a sputtering method to form a cathode. Thereafter, the substrate was transferred to a glove box, and sealed with a glass cap containing a desiccant in a nitrogen atmosphere to obtain an organic EL device.

A voltage application device was connected to the obtained organic EL device, and its characteristics were evaluated. The current-voltage characteristics were measured with a microammeter “4140B” manufactured by Hewlett-Packard Company, and the chromaticity was evaluated using “SR-3” manufactured by Topcon. The emission luminance was measured with “BM7” manufactured by Topcon Corporation. The efficiency, voltage, and CIE chromaticity coordinates at the time of display of 1000 cd / m ² are 6.4 cd / A, 3.2 V, and (0.36, 0.36), respectively. Was.

Next, the emission spectrum at a low current density (0.01 mA / cm ² ) was evaluated. When the peak height of the emission spectrum derived from the red emission dopant was set to 1.0, the respective peak heights of the blue emission dopant and the green emission dopant were evaluated. "X" when the peak height was less than 0.1, "△" when the peak height was 0.1 or more and less than 0.5, and "○" when the peak height was 0.5 or more. That is, when the peak heights of blue light emission and green light emission are sufficiently high, it can be said that good white light emission can be obtained even at a low current density, that is, at a low luminance. Table 4 shows the results.

Further, a continuous driving test was performed at an initial luminance of 2000 cd / m ² , and the luminance deterioration rate after 100 hours had elapsed was measured. Table 4 shows the results.

(Examples 3 to 6, Comparative Examples 1 to 3)
An organic EL device was produced in the same manner as in Example 2, except that the first light emitting layer, the intermediate layer, and the second light emitting layer of Example 2 were changed to the compounds shown in Table 4. The characteristics of the obtained organic EL device were measured and evaluated in the same manner as in Example 2. Table 4 shows the results.

{Circle around (2)} As shown in Examples 2 to 7, in the organic EL device of the present invention, excellent durability characteristics and white light emission with a good balance of red, green, and blue in a low luminance range could be confirmed. On the other hand, in Comparative Example 1, white light emission with good balance could be confirmed, but the durability was not excellent. This is because the HOMO level of the intermediate layer is small and the material of the intermediate layer is HT7 (amine compound), not hydrocarbon. In Comparative Example 2, a decrease in durability was confirmed. This is due to the fact that the interlayer material is not a hydrocarbon. Further, in Comparative Example 3, light emission with good balance could not be confirmed. This is presumably because energy is transferred from the second light emitting layer (blue light emitting layer) to the first light emitting layer (red / green light emitting layer) because the intermediate layer is not present.

(Examples 8 to 11, Comparative Example 4)
An organic EL device was produced in the same manner as in Example 1, except that the first light emitting layer, the intermediate layer, and the second light emitting layer of Example 2 were appropriately changed to the compounds, film thicknesses, and concentrations shown in Table 5. . The characteristics of the obtained organic EL device were measured and evaluated in the same manner as in Example 1. Table 5 shows the results.

(Examples 12 and 14)
The first light-emitting layer / intermediate layer / second light-emitting layer of Example 2 was changed to a first light-emitting layer / intermediate layer / second light-emitting layer / third light-emitting layer as shown in Table 6 to obtain a compound. An organic EL device was produced in the same manner as in Example 2, except that the concentration and the concentration were changed as shown in Table 6. However, the thickness is 10 nm / 5 nm / 10 nm / 5 nm = first light emitting layer / intermediate layer / second light emitting layer / third light emitting layer. The characteristics of the obtained organic EL device were measured and evaluated in the same manner as in Example 2. Table 7 shows the results.

As shown in Examples 8 to 14, in the organic EL device of the present invention, excellent durability characteristics and white light emission with a good balance of red, green, and blue in a low luminance range could be confirmed. On the other hand, in Comparative Example 4, light emission with good balance could not be confirmed. This is because energy is transferred from the first light emitting layer (blue light emitting layer) to the second light emitting layer (red green light emitting layer) because there is no intermediate layer.

(Example 15)
In this embodiment, an anode, a hole injection layer, an electron blocking layer, a hole transport layer, a first light emitting layer, an intermediate layer, a second light emitting layer, a third light emitting layer, a hole blocking layer, an electron transport layer An organic EL device having a bottom emission structure in which a layer, an electron injection layer, and a cathode were sequentially formed was manufactured. Specifically, first, an ITO film was formed on a glass substrate, and a desired patterning process was performed to form an ITO electrode (anode). At this time, the thickness of the ITO electrode was set to 100 nm. Next, vacuum deposition was performed by resistance heating in a 1.33 × 10 ⁻⁴ Pa vacuum chamber, and an organic compound layer and a cathode shown in Table 8 below were continuously formed on the ITO electrode. At this time, the facing area between the anode and the cathode was set to 3 mm ² .

Then, the substrate was transferred to a glove box, and sealed with a glass cap containing a desiccant in a nitrogen atmosphere to obtain an organic EL device. The characteristics of the obtained organic EL device were measured and evaluated in the same manner as in Example 2. Table 9 shows the results.

(Examples 16 and 17, Comparative Examples 5 and 7)
An organic EL device was produced in the same manner as in Example 15 except that the first light emitting layer / intermediate layer / second light emitting layer / third light emitting layer of Example 15 were changed to the compounds shown in Table 9. The characteristics of the obtained organic EL device were measured and evaluated in the same manner as in Example 2. Table 10 shows the measurement results.

As in Examples 15 to 17, in the organic EL device of the present invention, excellent durability characteristics and well-balanced white light emission could be confirmed. On the other hand, in Comparative Example 5, white light emission with good balance could be confirmed, but the durability was not excellent. This is due to the small HOMO level of the intermediate layer. In Comparative Example 6, a decrease in durability was confirmed. This is because the blue light emitting layer is not electron trapping. Furthermore, in Comparative Example 7, light emission with good balance could not be confirmed. This is because the intermediate layer has a low S ₁ level, and energy is transferred from the second light emitting layer (blue light emitting layer) to the first light emitting layer or the third light emitting layer (red or green light emitting layer). Can be

The present invention is not limited to the above-described embodiment, and various changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, the following claims are appended to make the scope of the present invention public.

This application claims priority based on Japanese Patent Application No. 2018-128017 filed on July 5, 2018 and Japanese Patent Application No. 2019-117143 filed on June 25, 2019, The entire contents of the description are incorporated herein.

Claims

At least an anode, a first light emitting layer, an intermediate layer, a second light emitting layer, and a cathode are provided in this order, and the intermediate layer is disposed between the first light emitting layer and the second light emitting layer. Organic EL element,
The first light-emitting layer contains a first host and a first dopant,
The second light-emitting layer contains a second host and a second dopant,
The intermediate layer contains an aromatic hydrocarbon compound,
The following relationship (a) holds between the first host and the first dopant,
The following relationship (b) holds between the second host and the second dopant,
An organic EL device wherein the following relationship (c) is established between the intermediate layer material and the first host.
(A) LUMO (H1)> LUMO (D1)
(B) LUMO (H2)> LUMO (D2)
(C) HOMO (H1) ≧ HOMO (IL)
[In the above (a) to (c), LUMO (H1), LUMO (D1), LUMO (H2), and LUMO (D2) are the first host, the first dopant, the second host, and the second dopant, respectively. HOMO (H1) and HOMO (IL) represent the energy levels of the HOMO of the first host and the intermediate layer material, respectively. ]
The organic EL device according to claim 1, wherein the energy level of the lowest excited singlet of the intermediate layer is 2.58 eV or more.
The aromatic hydrocarbon compound has a molecular structure in which one or more aromatic hydrocarbons selected from benzene, naphthalene, fluorene, benzofluorene, phenanthrene, anthracene, chrysene, triphenylene, pyrene, fluoranthene, and benzofluoranthene are bonded. 3. The organic EL device according to claim 1, wherein
3. The organic EL device according to claim 1, wherein the first host and the second host are hydrocarbons.
The organic EL device according to any one of claims 1 to 4, wherein the first dopant and the second dopant are fluorescent dopants.
6. The organic EL device according to claim 1, wherein the first dopant and the second dopant are compounds having a fluoranthene skeleton and having no substituted amino group. 7.
A third light emitting layer is provided between the second light emitting layer and the cathode, adjacent to the second light emitting layer,
The third light-emitting layer contains a third host and a third dopant that emits fluorescence,
The organic EL device according to any one of claims 1 to 6, wherein the following relationship (d) is established between the third host and the third dopant.
(D) LUMO (H3)> LUMO (D3)
[In the above (d), LUMO (H3) and LUMO (D3) represent the energy levels of the LUMO of the third host and the third dopant, respectively. ]
8. The organic EL device according to claim 7, wherein the first dopant emits red light, the second dopant, and the third dopant emit blue light while the other emits green light.
Between the anode and the first light emitting layer, having a third light emitting layer adjacent to the first light emitting layer,
The third light-emitting layer contains a third host and a third dopant that emits fluorescence,
The organic EL device according to any one of claims 1 to 6, wherein the following relationship (d) is established between the third host and the third dopant.
(D) LUMO (H3)> LUMO (D3)
[In the above (d), LUMO (H3) and LUMO (D3) represent the energy levels of the LUMO of the third host and the third dopant, respectively. ]
10. The organic EL device according to claim 9, wherein the first dopant emits green light, the second dopant emits blue light, and the third dopant emits red light.
The first light-emitting layer contains a third dopant that emits fluorescence,
The organic EL device according to any one of claims 1 to 6, wherein the following relationship (e) is established between the first host and the third dopant.
(E) LUMO (H1)> LUMO (D3)
[In the above (e), LUMO (D3) represents the energy level of LUMO of the third dopant. ]
The organic EL device according to claim 11, wherein the second dopant emits blue light, one of the first dopant and the third dopant emits red light, and the other emits green light.
The organic EL device according to any one of claims 7 to 12, wherein the third host is a hydrocarbon.
The organic EL device according to any one of claims 7 to 13, wherein the third dopant is a compound having a fluoranthene skeleton and having no substituted amino group.
The organic EL device according to any one of claims 1 to 14, wherein the following relationship (f) is established between the first host and the first dopant.
(F) HOMO (H1) <HOMO (D1)
[In the above (f), HOMO (H1) and HOMO (D1) represent the energy levels of the HOMO of the first host and the first dopant, respectively. ]
The organic EL device according to any one of claims 1 to 15, wherein the following relationship (g) is established between the second host and the second dopant.
(G) HOMO (H2)> HOMO (D2)
[In the above (g), HOMO (H2) and HOMO (D2) represent the energy levels of the HOMO of the second host and the second dopant, respectively. ]
17. The organic EL device according to claim 1, wherein the following relationship (h) is satisfied between the first host and the first dopant.
(H) LUMO (H1) -LUMO (D1)> HOMO (D1) -HOMO (H1)
[In the above (h), HOMO (D1) represents the energy level of the HOMO of the first dopant. ]
A display device having a plurality of pixels, wherein the pixels include the organic EL element according to any one of claims 1 to 17, and an active element connected to the organic EL element. Display device.
A foldable display device comprising: a flexible substrate; and a display unit disposed on the flexible substrate, wherein the display unit includes the organic EL element according to claim 1. And an active element connected to the organic EL element.
An optical device having a plurality of lenses, an image sensor that receives light that has passed through the optical unit, and a display unit that displays an image, wherein the display unit has an image captured by the image sensor. An imaging device, comprising: a display unit for displaying an image, wherein the display unit includes the organic EL element according to claim 1.
18. A communication device having a display unit and a communication unit, wherein the display unit includes the organic EL element according to claim 1.
A lighting device having a light source and a light diffusion unit, wherein the light source includes the organic EL element according to any one of claims 1 to 17.
A lighting device having a light source, comprising: an optical film on a light emitting side of the light source; wherein the light source includes the organic EL element according to claim 1. .
A lamp comprising the organic EL element according to any one of claims 1 to 17, and a protection member for protecting the organic EL element.
移動 A moving body having a body and a lamp provided on the body, wherein the lamp has the organic EL element according to any one of claims 1 to 17.