阅读说明：本技术 有机电场发光元件 (Organic electroluminescent element ) 是由 小川淳也 池永裕士 上田季子 于 2020-03-16 设计创作，主要内容包括：本发明提供一种尽管为低驱动电压,效率也高且具有高的驱动稳定性的有机EL元件。所述有机EL元件的特征在于：至少一个发光层包含蒸镀层,所述蒸镀层含有选自通式(1)所表示的吲哚并咔唑化合物中的第一主体与选自下述通式(2)所表示的双咔唑化合物中的第二主体、以及发光性掺杂剂材料。此处,m与n为重复数,为0～4的整数,且m+n≧2。Ar～(2)与Ar～(3)为芳香族烃基、或芳香族烃基的2个～3个连结而成的基,且至少一者为缩合芳香族烃基。(The present invention provides an organic EL element having high efficiency and high driving stability in spite of a low driving voltage. The organic EL element is characterized in that: at least one of the light-emitting layers includes a vapor deposition layer containing a first host selected from indolocarbazole compounds represented by general formula (1), a second host selected from biscarbazole compounds represented by general formula (2), and a light-emitting dopant material. Here, m and n are the number of repetitions, and are integers of 0 to 4, and m + n ≧ 2. Ar (Ar) 2 And Ar 3 Is an aromatic hydrocarbon group or a group formed by connecting 2 to 3 aromatic hydrocarbon groups,and at least one is a condensed aromatic hydrocarbon group.)

1. An organic electroluminescent element comprising one or more light-emitting layers between an anode and a cathode facing each other, characterized in that: at least one of the light-emitting layers includes a vapor deposition layer containing a first host selected from compounds represented by the following general formula (1), a second host selected from compounds represented by the following general formula (2), and a light-emitting dopant material,

[ solution 1]

Here, ring A is an aromatic hydrocarbon ring represented by formula (1a), ring B is a heterocyclic ring represented by formula (1B), ring A and ring B are each condensed at an arbitrary position with the adjacent rings,

Ar¹is phenyl, biphenyl or terphenyl,

r is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms,

a. b and c each independently represent an integer of 0 to 3,

m and n represent a repetition number, and each independently represents an integer of 0 to 4; wherein m + n is not equal to n, and m + n is ≧ 2;

[ solution 2]

Here, Ar²And Ar³Independently represent an aromatic hydrocarbon group having 6 to 14 carbon atoms or a linked aromatic group in which 2 to 3 of the aromatic hydrocarbon groups are linked, and Ar²And Ar³At least one of (a) is a condensed aromatic hydrocarbon group.

2. The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3),

[ solution 3]

Here, Ar²And Ar³And Ar of the general formula (2)²And Ar³Are the same meaning.

3. The organic electroluminescent element according to claim 1, wherein Ar is²Is naphthyl or phenanthryl.

4. The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by any one of the following general formulae (4) to (9),

[ solution 4]

Here, Ar¹R, a-c, m and n are the same as those in the general formula (1).

5. The organic electroluminescent element according to claim 1, wherein the proportion of the first host is more than 20 wt% and less than 55 wt% with respect to the total of the first host and the second host.

6. The organic electroluminescent element according to claim 1, wherein the light-emitting dopant material is an organic metal complex comprising at least one metal selected from the group consisting of ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold.

7. The organic electroluminescent element according to claim 1, wherein the light-emitting dopant material is a thermally activated delayed fluorescence emission dopant material.

8. The organic electroluminescent element according to claim 1, wherein a hole-blocking layer containing a compound represented by the general formula (1) is provided adjacent to the light-emitting layer.

9. A method for manufacturing an organic electroluminescent element, comprising: a step of mixing a first host and a second host to prepare a pre-mixture and then evaporating a host material containing the pre-mixture to form a light-emitting layer when manufacturing the organic electroluminescent element according to any one of claims 1 to 8.

10. The method of claim 9, wherein the difference between the 50% weight reduction temperatures of the first body and the second body is within 20 ℃.

Technical Field

The present invention relates to an organic Electroluminescence (EL) element. More specifically, the present invention relates to an organic EL element having a light-emitting layer including a first host, a second host, and a light-emitting dopant material.

Background

By applying a voltage to the organic EL element, holes are injected from the anode into the light-emitting layer, and electrons are injected from the cathode into the light-emitting layer. In the light-emitting layer, the injected holes and electrons recombine to generate excitons. At this time, according to the statistical rule of the electron spin, the ratio of 1: the ratio of 3 generates singlet excitons and triplet excitons. The limit of the internal quantum efficiency of a fluorescent light-emitting organic EL device using light emission using singlet excitons can be said to be 25%. On the other hand, it is known that when a phosphorescent organic EL element using light emission of triplet excitons efficiently performs intersystem crossing (intersystem crossing) from singlet excitons, the internal quantum efficiency is improved to 100%.

However, the increase in lifetime of a phosphorescent organic EL device is a technical problem.

Recently, high-efficiency organic EL devices using delayed fluorescence have been developed. For example, patent document 1 discloses an organic EL device using a Triplet-Triplet Fusion (TTF) mechanism, which is one of mechanisms for delaying fluorescence. The TTF mechanism is a mechanism utilizing a phenomenon in which singlet excitons are generated by collision of two triplet excitons, and is thought to theoretically improve the internal quantum efficiency to 40%. However, since the efficiency is low as compared with a phosphorescent organic EL device, further efficient improvement is required.

On the other hand, patent document 2 discloses an organic EL element using a Thermally Activated Delayed Fluorescence (TADF) mechanism. The TADF mechanism is a mechanism utilizing the following phenomenon: in a material having a small energy difference between the singlet energy level and the triplet energy level, an inverse intersystem crossing (inversion intersystem crossing) from the triplet exciton to the singlet exciton occurs; it is thought that the internal quantum efficiency is theoretically improved to 100%. However, further improvement in lifetime characteristics is required similarly to the phosphorescent type element.

Documents of the prior art

Patent document

Patent document 1: WO2010/134350A

Patent document 2: WO2011/070963A

Patent document 3: WO2008/056746A

Patent document 4: japanese patent laid-open No. 2003-133075

Patent document 5: WO2013/062075A

Patent document 6: US2014/0374728A

Patent document 7: US2014/0197386A

Patent document 8: US2015/0001488A

Patent document 9: US2015/0236262A

Patent document 10: WO2016/194604A

Patent document 11: WO2011/136755A

Patent document 3 discloses the use of indolocarbazole compounds as host materials. Patent document 4 discloses the use of a biscarbazole compound as a host material.

Patent documents 5 and 6 disclose that a biscarbazole compound is used as a mixed host. Patent documents 7, 8, 9, and 10 disclose the use of an indolocarbazole compound and a biscarbazole compound as a mixed host.

Patent document 11 discloses the use of a host material in which a plurality of types of hosts including an indolocarbazole compound are mixed in advance.

However, none of them is sufficient, and further improvement is desired.

Disclosure of Invention

In order to apply an organic EL element to a display element such as a flat panel display (flat panel display) or a light source, it is necessary to improve the light emission efficiency of the element and sufficiently ensure stability in driving. The purpose of the present invention is to provide an organic EL element which has high efficiency and high driving stability despite a low driving voltage.

The present invention is an organic EL element including one or more light-emitting layers between an anode and a cathode facing each other, the organic EL element including: at least one of the light-emitting layers includes a vapor deposition layer containing a first host selected from compounds represented by the following general formula (1), a second host selected from compounds represented by the following general formula (2), and a light-emitting dopant material.

[ solution 1]

Here, ring A is an aromatic hydrocarbon ring represented by formula (1a), ring B is a heterocyclic ring represented by formula (1B), ring A and ring B are each condensed at an arbitrary position with the adjacent rings,

Ar¹is phenyl, biphenyl or terphenyl,

r is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms,

a. b and c each independently represent an integer of 0 to 3,

m and n represent a repetition number, and each independently represents an integer of 0 to 4. Wherein m is not n, and m + n ≧ 2.

[ solution 2]

Here, Ar²And Ar³Represents an aromatic hydrocarbon group having 6 to 14 carbon atoms or a group formed by connecting 2 to 3 of the aromatic hydrocarbon groups, and Ar²And Ar³At least one of them represents a condensed aromatic hydrocarbon group.

Preferred examples of the general formula (2) include general formula (3).

[ solution 3]

Preferred embodiments of the general formula (1) include general formulae (4) to (9), preferably general formula (4), general formula (5), general formula (6), or general formula (7), and more preferably general formula (4).

[ solution 4]

The first body and the second body are preferably used by premixing before vapor deposition. Preferably, the difference between the 50% weight reduction temperatures of the first body and the second body is within 20 ℃, or the proportion of the first body to the total of the first body and the second body is more than 20 wt% and less than 55 wt%.

The luminescent dopant material may be a phosphorescent luminescent dopant material, a fluorescent luminescent dopant material, or a thermally activated delayed fluorescent luminescent dopant material. As the phosphorescent dopant material, an organic metal complex containing at least one metal selected from ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold is cited.

In the organic EL element, it is preferable that a hole blocking layer is provided adjacent to the light-emitting layer, and the compound represented by the general formula (1) is contained in the hole blocking layer.

In addition, the present invention is a method for manufacturing an organic electroluminescence element, including: and a step of mixing the first host and the second host to form a premix, and then depositing a host material containing the premix by vapor deposition to form a light-emitting layer in the production of the organic electroluminescent element.

In order to improve device characteristics, it is necessary to increase the durability of the material used in the organic layer against electric charges, and particularly in the light-emitting layer, it is important to suppress leakage of excitons and electric charges to the peripheral layer. For suppressing the leakage of the charge/exciton, it is effective to improve the shift of the light emitting region in the light emitting layer, and for this reason, it is necessary to control the both charge (electron/hole) injection amount to the light emitting layer or the both charge transport amount in the light emitting layer to a preferable range.

Here, the indolocarbazole compound of the general formula (1) has high skeleton stability, and both charge injection transportability can be controlled to some extent by an isomer or a substituent, but it is difficult to control both charge injection transportability to a preferable range as described above separately. On the other hand, the biscarbazole compound of the general formula (2) can control the charge injection transportability at a high level by changing the kind and number of substituents. Further, the biscarbazole compound has high amorphous stability and high skeleton stability as in the indolocarbazole compound. Therefore, by using the indolocarbazole compound and the biscarbazole compound in a mixture, the amount of charge injection into the organic layer can be adjusted to a preferable range, and more favorable device characteristics can be expected. In particular, in the case of a delayed fluorescence EL element or a phosphorescence EL element, since the minimum excited triplet energy sufficiently high for the excitation energy generated by being confined in the light-emitting layer is present, it is possible to realize high efficiency and long lifetime at a low voltage without energy flowing out from the light-emitting layer.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL element.

Detailed Description

The organic EL element of the present invention has one or more light-emitting layers between an anode and a cathode facing each other, and at least one of the light-emitting layers includes a vapor deposition layer containing a first host, a second host, and a luminescent dopant material. The vapor deposition layer may be made by vacuum vapor deposition. The first host is a compound represented by the general formula (1), and the second host is a compound represented by the general formula (2). The organic EL element has an organic layer including a plurality of layers between an anode and a cathode facing each other, at least one of the plurality of layers is a light-emitting layer, and the number of the light-emitting layers may be plural.

The general formula (1) will be described.

Ring A is an aromatic hydrocarbon ring represented by formula (1a), ring B is a heterocyclic ring represented by formula (1B), and ring A and ring B are condensed at arbitrary positions with adjacent rings, respectively.

Ar¹Represents phenyl, biphenyl or terphenyl. Preferably phenyl or biphenyl, more preferably phenyl. Here, biphenyl is a group represented by-Ph-Ph, and terphenyl is a group represented by-Ph-Ph or Ph (-Ph) -Ph. Here, Ph is a phenyl group, a phenylene group or the like.

R independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms. Preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a phenyl group or an aromatic heterocyclic group having 3 to 9 carbon atoms. More preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a phenyl group or an aromatic heterocyclic group having 3 to 6 carbon atoms.

Specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like. Preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms or the aromatic heterocyclic group having 3 to 12 carbon atoms include: an aromatic group formed by removing 1H from benzene, naphthalene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, oxazole, oxadiazole, quinoline, isoquinoline, quinoxaline, quinazoline, oxadiazole, thiadiazole, benzotriazine, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, or carbazole. Preferred examples thereof include: aromatic groups derived from benzene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, oxazole, oxadiazole, quinoline, isoquinoline, quinoxaline, quinazoline, oxadiazole, thiadiazole, benzotriazine, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, or benzothiadiazole. More preferably, the following are listed: an aromatic group derived from benzene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, oxazole, or oxadiazole.

a. b and c represent the number of substitution, and each independently represents an integer of 0 to 3, preferably 0 or 1. m and n represent a repetition number, each independently represents an integer of 0 to 4, and m does not become n. Here, m + n is preferably an integer of 2 or more, and more preferably an integer of 2 or 3.

Specific examples of the compound represented by the general formula (1) are shown below, but the compound is not limited to these exemplified compounds.

[ solution 5]

[ solution 6]

[ solution 7]

[ solution 8]

[ solution 9]

[ solution 10]

[ solution 11]

[ solution 12]

Next, the general formula (2) as the second main body and the general formula (3) as a preferred embodiment thereof will be described. In the general formulae (2) and (3), the common symbols have the same meaning.

Ar²And Ar³Represents an aromatic hydrocarbon group having 6 to 14 carbon atoms or a linked aromatic group in which 2 to 3 of the aromatic hydrocarbon groups are linked. Preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, Ar²And Ar³At least one of (a) is a condensed aromatic hydrocarbon group.

Ar²And Ar³Specific examples of (A) include: an aromatic group or a linked aromatic group formed by extracting 1H from an aromatic hydrocarbon such as benzene, naphthalene, anthracene, phenanthrene, or fluorene, or a compound in which 2 aromatic rings of the aromatic hydrocarbon are linked. Preferred examples thereof include: an aromatic group derived from benzene, naphthalene, anthracene or phenanthrene or a linked aromatic group derived from 2 linked aromatic groups of these aromatic groups, and more preferably an aromatic group derived from benzene, naphthalene or phenanthrene. Ar (Ar)³Further preferably naphthyl or phenanthreneAnd (4) a base. The aromatic group or the linking aromatic group may have a substituent, and the preferred substituent is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

Here, the linking aromatic group is represented by, for example, -Ar⁴-Ar⁵Such an equation is shown. Here, Ar⁴、Ar⁵Independently an aromatic hydrocarbon group having 6 to 14 carbon atoms. Ar (Ar)⁴Is a divalent or trivalent radical, Ar⁵Is monovalent. The aromatic groups constituting the linking aromatic group may be the same or different.

Specific examples of the compounds represented by general formulae (2) to (3) are shown below, but the compounds are not limited to these exemplified compounds.

[ solution 13]

[ solution 14]

[ solution 15]

[ solution 16]

[ solution 17]

By using a first host selected from the compounds represented by the general formula (1) and a second host selected from the compounds represented by the general formula (2) as host materials of a light-emitting layer, an excellent organic EL element can be provided.

The first host and the second host may be used by vapor deposition from different vapor deposition sources, but it is preferable that a premix is prepared by premixing before vapor deposition, and the premix is simultaneously vapor deposited from one vapor deposition source to form a light-emitting layer. In this case, a light-emitting dopant material necessary for forming a light-emitting layer or another host used as needed may be mixed in the pre-mixture, but when there is a large difference in temperature to a desired vapor pressure, vapor deposition may be performed from another vapor deposition source.

In addition, regarding the mixing ratio (weight ratio) of the first body to the second body, the ratio of the first body may be 20% to 60%, preferably more than 20% and less than 55%, more preferably 40% to 50%, with respect to the total of the first body and the second body.

Next, the structure of the organic EL device of the present invention will be described with reference to the drawings, but the structure of the organic EL device of the present invention is not limited thereto.

Fig. 1 is a sectional view showing a configuration example of a general organic EL device used in the present invention, in which 1 shows a substrate, 2 shows an anode, 3 shows a hole injection layer, 4 shows a hole transport layer, 5 shows a light emitting layer, 6 shows an electron transport layer, and 7 shows a cathode. The organic EL device of the present invention may have an exciton-blocking layer adjacent to the light-emitting layer, or an electron-blocking layer between the light-emitting layer and the hole-injecting layer. The exciton blocking layer may be inserted into either the cathode side or the cathode side of the light-emitting layer, or may be inserted into both sides. In the organic EL element of the present invention, the anode, the light-emitting layer, and the cathode are provided as essential layers, but a hole injection transport layer, an electron injection transport layer, and a hole blocking layer may be provided between the light-emitting layer and the electron injection transport layer, in addition to the essential layers. The hole injection transport layer refers to either or both of the hole injection layer and the hole transport layer, and the electron injection transport layer refers to either or both of the electron injection layer and the electron transport layer.

In the structure opposite to that of fig. 1, that is, the cathode 7, the electron transport layer 6, the light-emitting layer 5, the hole transport layer 4, and the anode 2 may be sequentially stacked on the substrate 1, and in this case, the layers may be added or omitted as necessary.

A substrate

The organic EL element of the present invention is preferably supported on a substrate. The substrate is not particularly limited as long as it is a substrate conventionally used for an organic EL element, and for example, a substrate made of glass, transparent plastic, quartz, or the like can be used.

-anode-

As the anode material in the organic EL element, a material containing a metal, an alloy, a conductive compound, or a mixture of these, which has a large work function (work function), can be preferably used. Specific examples of such electrode materials include metals such as Au, CuI, Indium Tin Oxide (ITO), and SnO₂And conductive transparent materials such as ZnO. In addition, IDIXO (In) can also be used₂O₃-ZnO), and the like, and can be formed into a transparent conductive film. The anode may be formed by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering, and forming a pattern of a desired shape by photolithography, or may be formed by interposing a mask of a desired shape during vapor deposition or sputtering of the electrode materials when pattern accuracy is not required (about 100 μm or more). Alternatively, when a coatable substance such as an organic conductive compound is used, a wet film forming method such as a printing method or a coating method may be used. When light emission is extracted from the anode, the transmittance is preferably set to be higher than 10%, and the sheet resistance of the anode is preferably several hundred Ω/γ or less. The film thickness depends on the material, and is usually selected from the range of 10nm to 1000nm, preferably 10nm to 200 nm.

-cathode-

On the other hand, as the cathode material, a material containing a metal (electron-injecting metal) having a small work function (4eV or less), an alloy, a conductive compound, or a mixture of these can be used. Specific examples of such electrode materials include: sodium, sodium-potassium alloys, magnesium, lithium, magnesium/copper mixtures, magnesium/silver mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures, aluminum/aluminum oxide (Al)₂O₃) MixingSubstances, indium, lithium/aluminum mixtures, rare earth metals, and the like. Of these, from the viewpoint of electron injection property and durability against oxidation and the like, a mixture of an electron-injecting metal and a second metal which is a metal having a higher and more stable work function than the electron-injecting metal is preferable, and examples thereof include a magnesium/silver mixture, a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide mixture, a lithium/aluminum mixture, and aluminum. The cathode may be fabricated by: these cathode materials are formed into thin films by a method such as vapor deposition or sputtering. Further, the sheet resistance of the cathode is preferably several hundred Ω/γ or less, and the film thickness is usually selected in the range of 10nm to 5 μm, preferably 50nm to 200 nm. Further, in order to transmit the emitted light, it is advantageous that the emission luminance is improved if either the anode or the cathode of the organic EL element is transparent or translucent.

Further, by forming the metal in the cathode in a film thickness of 1nm to 20nm and then forming the conductive transparent material mentioned in the description of the anode thereon, a transparent or translucent cathode can be produced, and by applying the above method, an element having both the anode and the cathode having transparency can be produced.

-a light-emitting layer-

The light-emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from the anode and the cathode, and the light-emitting layer contains an organic light-emitting dopant material and a host material.

As the host material in the light-emitting layer, a first host represented by general formula (1) and a second host represented by general formula (2) are used. Further, one kind of known host material may be used or a plurality of kinds may be used in combination, and the amount used may be 50 wt% or less, preferably 25 wt% or less, based on the total amount of the host materials.

The first body and the second body may be simultaneously evaporated from one evaporation source by performing evaporation from different evaporation sources, or may be premixed before evaporation to prepare a premix.

When the first body and the second body are premixed and used, the composition can be manufactured with good reproducibilityThe organic EL element having the characteristics is desirably 50% weight loss temperature (T)₅₀) The difference of (a) is small. The 50% weight loss temperature is a temperature at which 50% weight loss occurs when the temperature is raised from room temperature to 550 ℃ at a rate of 10 ℃ per minute in a Thermogravimetric-Differential Thermal Analysis (TG-DTA) measurement under a reduced pressure of nitrogen flow (50 Pa). It is considered that the vaporization caused by evaporation or sublimation occurs most intensely in the vicinity of the temperature.

Preferably, the difference between the first body and the second body is within 20 ℃, more preferably within 15 ℃ of the 50% weight loss temperature. As the premixing method, a known method such as pulverization and mixing can be used, and it is desirable to mix them uniformly as much as possible.

In the case of using a phosphorescent light-emitting dopant as a light-emitting dopant material, the phosphorescent light-emitting dopant may be a phosphorescent light-emitting dopant containing an organic metal complex including at least one metal selected from ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. Specifically, iridium complexes described in journal of the american chemical society (j.am. chem. soc.) 2001, 123, 4304 or japanese patent publication No. 2013-53051 can be suitably used, but are not limited thereto.

The phosphorescent dopant material may contain only one kind of material in the light-emitting layer, or may contain two or more kinds of materials. The content of the phosphorescent dopant material is preferably 0.1 to 30 wt%, more preferably 1 to 20 wt%, relative to the host material.

The phosphorescent dopant material is not particularly limited, and specific examples thereof include the following.

[ solution 18]

[ solution 19]

In using fluorescenceWhen the light-emitting dopant is used as the light-emitting dopant material, the fluorescent light-emitting dopant is not particularly limited, and examples thereof include: benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, azino derivatives, pyrrolidine derivatives, cyclopentadiene derivatives, distyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, styrylamine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylene compounds, metal complexes of 8-hydroxyquinoline derivatives or metal complexes of pyrrolidylene derivatives, rare earth complexes, various metal complexes represented by transition metal complexes, and the like, polythiophenes, benzoguanazoles, styrylbenzene derivatives, and the like, Polymer compounds such as polyphenylene and polyphenylene vinylene, and organic silane derivatives. Preferred examples thereof include: condensed aromatic derivatives, styryl derivatives, diketopyrrolopyrrole derivatives, oxazine derivatives, pyrromethene metal complexes, transition metal complexes or lanthanide complexes, more preferably as follows: naphthalene, pyrene,Triphenylene, benzo [ c ]]Phenanthrene, benzo [ a ]]Anthracene, pentacene, perylene, fluoranthene, acenaphthofluoranthene, dibenzo [ a, j ] s]Anthracene, dibenzo [ a, h ]]Anthracene, benzo [ a ]]Naphthalene, hexacene, naphtho [2,1-f ]]Isoquinoline, alpha-naphthophenanthridine, phenanthrooxazole, quinolino [6,5-f]Quinoline, benzonaphthothiophene, and the like. These may also have an alkyl group, an aryl group, an aromatic heterocyclic group, or a diarylamino group as a substituent.

The fluorescent light-emitting dopant material may contain only one kind of the light-emitting layer, or may contain two or more kinds of the light-emitting layer. The content of the fluorescent light-emitting dopant material is preferably 0.1% to 20%, more preferably 1% to 10%, relative to the host material.

When a thermally activated delayed fluorescence emission dopant is used as a light-emitting dopant material, the thermally activated delayed fluorescence emission dopant is not particularly limited, and examples thereof include metal complexes such as tin complexes and copper complexes, indolocarbazole derivatives described in WO2011/070963, cyanobenzene derivatives and carbazole derivatives described in Nature 2012, 492, 234, phenazine derivatives, oxadiazole derivatives, triazole derivatives, sulfone derivatives, phenoxazine derivatives, and acridine derivatives described in Nature Photonics 2014, 8, 326.

The thermally activated delayed fluorescence emission dopant material is not particularly limited, and specific examples thereof include the following.

[ solution 20]

The thermally activated delayed fluorescence emission dopant material may contain only one kind of the emission layer, or may contain two or more kinds of the emission layers. The thermally activated delayed fluorescence emission dopant may be mixed with a phosphorescent emission dopant or a fluorescence emission dopant. The content of the thermally activated delayed fluorescence emission dopant material is preferably 0.1% to 50%, more preferably 1% to 30%, relative to the host material.

Injection layer-

The injection layer is a layer provided between the electrode and the organic layer for the purpose of reducing the driving voltage or improving the emission luminance, and therefore, a hole injection layer and an electron injection layer may be present between the anode and the light-emitting layer or the hole transport layer, and between the cathode and the light-emitting layer or the electron transport layer. The injection layer may be provided as desired.

Hole-blocking layer-

The hole blocking layer has a function of an electron transport layer in a broad sense, and includes a hole blocking material having a function of transporting electrons and a significantly small ability of transporting holes, and can increase the recombination probability of electrons and holes in the light emitting layer by transporting electrons and blocking holes.

In the hole-blocking layer, a known hole-blocking layer material can be used, and preferably, a compound represented by the general formula (1) is contained.

Electron blocking layer

The electron blocking layer has a function of a hole transport layer in a broad sense, and can increase the probability of recombination of electrons and holes in the light emitting layer by transporting holes and blocking electrons.

As the material of the electron blocking layer, a known electron blocking layer material can be used, and a material of a hole transporting layer described later can be used as necessary. The thickness of the electron blocking layer is preferably 3nm to 100nm, more preferably 5nm to 30 nm.

Exciton blocking layer

The exciton blocking layer is a layer for blocking diffusion of excitons generated by recombination of holes and electrons in the light emitting layer to the charge transport layer, and by interposing this layer, excitons can be efficiently sealed in the light emitting layer, and the light emitting efficiency of the element can be improved. The exciton blocking layer may be interposed between two adjacent light emitting layers in an element in which two or more light emitting layers are adjacent.

As the material of the exciton blocking layer, a known exciton blocking layer material may be used. Examples thereof include 1, 3-dicarbazolylbenzene (mCP) and bis (2-methyl-8-quinolinolato) -4-phenylphenolaluminum (III) (BALq).

Hole transport layer

The hole transport layer contains a hole transport material having a function of transporting holes, and the hole transport layer may be provided in a single layer or multiple layers.

The hole-transporting material is a material having hole injection or transport properties and electron barrier properties, and may be either an organic material or an inorganic material. In the hole transport layer, any compound can be selected from conventionally known compounds and used. Examples of the hole transport material include: porphyrin derivatives, arylamine derivatives, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and electroconductive polymer oligomers, particularly thiophene oligomers, etc., preferably porphyrin derivatives, arylamine derivatives, and styrylamine derivatives, and more preferably arylamine compounds.

Electron transport layer

The electron transport layer contains a material having a function of transporting electrons, and the electron transport layer may be provided in a single layer or in multiple layers.

The electron transport material (which may also serve as a hole blocking material) may have a function of transporting electrons injected from the cathode to the light-emitting layer. In the electron transport layer, any compound can be selected from conventionally known compounds and used, and examples thereof include: polycyclic aromatic derivatives such as naphthalene, anthracene, phenanthroline, tris (8-hydroxyquinoline) aluminum (III) derivatives, phosphine oxide derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidene methane derivatives, anthraquinone dimethane and anthrone derivatives, bipyridine derivatives, quinoline derivatives, oxadiazole derivatives, benzimidazole derivatives, benzothiazole derivatives, indolocarbazole derivatives, and the like. Further, polymer materials in which these materials are introduced into a polymer chain or as the main chain of a polymer may be used.

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples, and can be carried out in various ways without departing from the spirit thereof.

Example 1

On a glass substrate on which an anode comprising ITO having a film thickness of 110nm was formed, vacuum deposition was performed in a degree of vacuum of 4.0X 10^-5Pa to laminate the films. First, HAT-CN was formed to a thickness of 25nm as a hole injection layer on ITO, and then NPD was formed to a thickness of 30nm as a hole transport layer. Next, HT-1 was formed to a thickness of 10nm as an electron blocking layer. Then, a compound 1-1 as a first host, a compound 2-1 as a second host, and a dopant for light emission are co-evaporated from different evaporation sourcesIr (ppy) of agent₃The light-emitting layer was formed to a thickness of 40 nm. At this time, in Ir (ppy)₃Becomes 10 wt%, the weight ratio of the first body to the second body becomes 30: co-evaporation was performed under the evaporation conditions of 70 deg.f. Next, ET-1 was formed to have a thickness of 20nm as an electron transport layer. Further, LiF was formed to have a thickness of 1nm as an electron injection layer on the electron transport layer. Finally, an organic EL element was fabricated by forming Al to a thickness of 70nm as a cathode on the electron injection layer.

Examples 2 to 14

An organic EL device was produced in the same manner as in example 1, except that the compounds shown in table 1 were used for the first host and the second host in example 1.

Examples 15 to 17

The first body and the second body are mixed in advance to make a pre-mixture, and the pre-mixture is co-evaporated from the same evaporation source.

In example 1, a first body (0.30g) and a second body (0.70g) were measured and mixed while being crushed in a mortar to obtain a premix, and an organic EL element was produced in the same manner as in example 1 except that the obtained premix was used.

Examples 18 to 23

The first body and the second body are mixed in advance to prepare a pre-mixture, and the pre-mixture is co-evaporated from the same evaporation source, thereby manufacturing an organic EL element provided with a hole blocking layer.

Organic EL devices were fabricated in the same manner as in examples 15 to 17, except that in examples 15 to 17, after the formation of the light-emitting layer, the compound 1-4 was formed to a thickness of 10nm as a hole-blocking layer and the ET-1 was formed to a thickness of 10nm as an electron-transporting layer.

The evaluation results of the fabricated organic EL devices are shown in table 1. In the table, the luminance, the driving voltage, and the luminous efficiency were obtained by setting the driving current to 20mA/cm²The value of time is the initial characteristic. LT70 is the time it takes for the initial luminance to decay to 70%, representing the lifetime characteristic.

[ Table 1]

Comparative example 1

An organic EL device was produced in the same manner as in example 1, except that the compound 1-1 was used alone as the main component in example 1. The thickness and the light-emitting dopant concentration of the light-emitting layer were the same as those in example 1.

Comparative examples 2 to 8

An organic EL device was produced in the same manner as in comparative example 1, except that the compounds shown in table 2 were used alone as the main component.

Comparative examples 9 to 10

An organic EL device was produced in the same manner as in example 1, except that compound a was used as the first host and compound 2-1 or compound 2-3 was used as the second host in example 1.

Comparative examples 11 to 12

Organic EL devices were produced in the same manner as in comparative examples 9 to 10, except that compound B was used as the first host in comparative examples 9 to 10.

Comparative examples 13 to 14

Organic EL devices were produced in the same manner as in comparative examples 9 to 10, except that compound C was used as the first host in comparative examples 9 to 10.

Comparative examples 15 to 16

Organic EL devices were produced in the same manner as in comparative examples 9 to 10, except that compound D was used as the first host in comparative examples 9 to 10.

The evaluation results of the fabricated organic EL devices are shown in table 2.

[ Table 2]

As is clear from table 1, examples 1 to 23 have improved power efficiency and life characteristics and exhibit good characteristics.

Example 24

On a glass substrate on which an anode comprising ITO having a film thickness of 110nm was formed, vacuum deposition was performed in a degree of vacuum of 4.0X 10^-5Pa to laminate the films. First, HAT-CN was formed to a thickness of 25nm as a hole injection layer on ITO, and then NPD was formed to a thickness of 45nm as a hole transport layer. Next, HT-1 was formed to a thickness of 10nm as an electron blocking layer. Then, a compound 1-1 as a first host, a compound 2-1 as a second host, and Ir (piq) as a light-emitting dopant are co-evaporated from different evaporation sources₂acac, the light-emitting layer was formed to a thickness of 40 nm. At this time, in Ir (piq)₂The co-evaporation was performed under evaporation conditions such that the acac concentration became 6.0 wt%. Then, ET-1 was formed to a thickness of 37.5nm as an electron transporting layer. Further, LiF was formed to have a thickness of 1nm as an electron injection layer on the electron transport layer. Finally, an organic EL element was fabricated by forming Al to a thickness of 70nm as a cathode on the electron injection layer.

Examples 25 to 37

An organic EL device was produced in the same manner as in example 24, except that the compounds shown in table 3 were used for the first host and the second host in example 24.

The evaluation results of the fabricated organic EL devices are shown in table 3. Here, LT95 is the time it takes for the initial luminance to decay to 95%, representing the lifetime characteristic.

[ Table 3]

Comparative example 17

An organic EL device was produced in the same manner as in example 24, except that in example 24, the compound 1-1 was used alone as the main component. The thickness and the light-emitting dopant concentration of the light-emitting layer were the same as those in example 24.

Comparative examples 18 to 24

An organic EL device was produced in the same manner as in comparative example 17, except that the compound shown in table 4 was used alone as the main component.

Comparative examples 25 to 26

An organic EL device was produced in the same manner as in example 24, except that in example 24, the compound a was used as the first host and the compound 2-1 or the compound 2-3 was used as the second host.

Comparative examples 27 to 28

Organic EL devices were produced in the same manner as in comparative examples 25 to 26, except that compound B was used as the first host in comparative examples 25 to 26.

Comparative examples 29 to 30

Organic EL devices were produced in the same manner as in comparative examples 25 to 26, except that compound C was used as the first host in comparative examples 25 to 26.

Comparative examples 31 to 32

Organic EL devices were produced in the same manner as in comparative examples 25 to 26, except that compound D was used as the first host in comparative examples 25 to 26.

The evaluation results of the fabricated organic EL devices are shown in table 4.

[ Table 4]

As is clear from table 3, the power efficiency and the life characteristics of examples 24 to 37 were improved, and the excellent characteristics were exhibited.

The compounds used in the examples are shown below.

[ solution 21]

Industrial applicability

In the organic electroluminescent element of the present invention, energy leakage in the self-light emitting layer is small, and high efficiency and long life can be achieved at low voltage.