阅读说明：本技术 延迟荧光材料及包含其的有机发光材料 (Delayed fluorescent material and organic light emitting material including the same ) 是由 金振珠 李俊烨 李豪中 洪玩杓 宋沃根 于 2018-07-27 设计创作，主要内容包括：本说明书涉及由化学式1构成的延迟荧光材料及包含其的有机发光元件。(The present specification relates to a delayed fluorescent material composed of chemical formula 1 and an organic light emitting element including the same.)

1. A delayed fluorescence material, comprising a compound represented by the following chemical formula 1:

chemical formula 1

In the chemical formula 1, the metal oxide is represented by,

r1 to R14 are the same as or different from each other, and each independently is hydrogen, deuterium, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amide group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boron group, a substituted or unsubstituted amine group, a substituted or unsubstituted arylphosphine group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

2. The delayed fluorescence material according to claim 1, wherein the triplet energy level of the compound represented by chemical formula 1 is 2.0eV or more.

3. The delayed fluorescence material according to claim 1, wherein the difference between the singlet state energy level and the triplet state energy level of the compound represented by chemical formula 1 is 0.3eV or less.

4. The delayed fluorescent material of claim 1, wherein the chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-3:

chemical formula 1-1

Chemical formula 1-2

Chemical formulas 1 to 3

In the chemical formulas 1-1 to 1-3,

r1 to R14 are the same as defined in the chemical formula 1.

5. The delayed fluorescence material according to claim 1, wherein the chemical formula 1 is selected from the following compounds:

6. an organic light-emitting element comprising: a first electrode, a second electrode provided so as to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers contain the delayed fluorescent material according to any one of claims 1 to 5.

7. The organic light-emitting element according to claim 6, wherein the organic layer comprises a light-emitting layer containing the delayed fluorescent material.

8. The organic light-emitting element according to claim 6, wherein the organic layer comprises a light-emitting layer containing the delayed fluorescence material as a dopant of the light-emitting layer.

Technical Field

The present application claims priority of korean patent application No. 10-2017-0095434, filed on 27.7.2017 with the korean patent office, the entire contents of which are incorporated herein by reference.

The present specification relates to a delayed fluorescence material and an organic light emitting element including the same.

Background

In order to commercialize an organic light emitting element, it is required to improve the efficiency of a light emitting material, and for this reason, research into phosphorescent and delayed fluorescent materials is being actively conducted. However, in the case of the above-mentioned fluorescent material, although high efficiency can be achieved, there is a problem that the price of the metal complex required for realizing phosphorescence is high and the lifetime is short.

In the case of Delayed Fluorescence materials, a concept of Thermally Activated Delayed Fluorescence (TADF) has recently been introduced, and a high-efficiency green fluorescent material which is both a fluorescent material and has high external quantum efficiency has been published. The concept of Thermally Activated Delayed Fluorescence (TADF) refers to a phenomenon in which fluorescence emission is realized by reverse energy transfer from an excited triplet state to an excited singlet state due to thermal activation, and since light emission occurs through a triplet path, delayed fluorescence is generally called from the viewpoint of emission having a long lifetime. The delayed fluorescent material can use both fluorescence and phosphorescence, and therefore, can solve the problem of external quantum efficiency of the conventional fluorescent material, and can solve the problem of the price of the phosphorescent material in that the material may not contain a metal complex.

Disclosure of Invention

Technical subject

The present specification provides a delayed fluorescence material and an organic light emitting element including the same.

Means for solving the problems

According to one embodiment of the present specification, there is provided a delayed fluorescence material composed of a compound represented by the following chemical formula 1.

[ chemical formula 1]

In the above-described chemical formula 1,

r1 to R14, which are the same or different from each other, are each independently hydrogen, deuterium, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amide group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group(s) ((R))Alkyl thioaxy), substituted or unsubstituted arylthio(s) ((R)Aryl thio), substituted or unsubstituted alkylsulfonyl(s) ((s) Alkyl sulfoxy), substituted or unsubstituted arylsulfonyl(s) ((s) Aryl sulfoxy), a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted arylphosphino group, a substituted or unsubstituted phosphinoxide group, a substituted or unsubstituted Aryl group, or a substituted or unsubstituted heteroaryl group.

In addition, according to one embodiment of the present specification, there is provided an organic light-emitting element including: the organic el display device includes a first electrode, a second electrode provided so as to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers include the delayed fluorescent material.

Effects of the invention

An organic light emitting element using a delayed fluorescence material composed of the compound represented by chemical formula 1 according to an embodiment of the present specification can achieve an improvement in efficiency, a low driving voltage, and/or an improvement in lifetime characteristics.

Drawings

Fig. 1 illustrates an organic light emitting element 10 according to an embodiment of the present description.

Fig. 2 is a graph showing NMR data of compound 1 according to an embodiment of the present specification.

Fig. 3 shows a UV-vis absorption spectrum, a photoluminescence spectrum in a solid state, and a photoluminescence spectrum in a Low-Temperature (Low-Temperature) state of compound 1 according to an embodiment of the present specification.

Fig. 4 is a cyclic voltammetry (cyclic voltammetry) chart of compound 1 according to an embodiment of the present description.

Fig. 5 is a graph showing NMR data of compound 2 according to an embodiment of the present specification.

Fig. 6 shows a UV-vis absorption spectrum, a photoluminescence spectrum in a solid state, and a photoluminescence spectrum in a Low-Temperature (Low-Temperature) state of compound 2 according to an embodiment of the present specification.

Fig. 7 is a cyclic voltammetry (cyclic voltammetry) graph of compound 2 according to an embodiment of the present description.

[ description of symbols ]

10: organic light emitting element

20: substrate

30: a first electrode

40: luminescent layer

50: second electrode

Detailed Description

According to an embodiment of the present specification, there is provided a delayed fluorescence material composed of the compound represented by the above chemical formula 1.

The compound represented by chemical formula 1 according to one embodiment of the present specification is easy in electron injection by introducing a cyano group and a triazine group that function as electron acceptors, and an organic light emitting element including the same as a delayed fluorescent material has characteristics of high efficiency and long life.

In addition, the compound represented by the above chemical formula 1 enhances electron injection characteristics by introducing a phenylene group substituted with a cyano group as a linking group between the triazine group and the carbazole group, and thus an organic light emitting element using the same as a light emitting layer can improve the efficiency of the element.

According to one embodiment of the present disclosure, when the cyano group of chemical formula 1 is located closer to the dicarbazole functioning as an electron Donor (Donor) than the triazine group functioning as an electron Acceptor (Acceptor), the delayed fluorescent material composed of the compound represented by chemical formula 1 has an effect of improving the lifetime of the element when applied to an organic light-emitting element.

In the present specification, delayed fluorescence means that excitons are excited from the triplet excited state (T)₁) Converting (converting) to singlet excited state (S)₁) And in the singlet excited state (S)₁) Fluorescence is emitted. The peak position of the emission spectrum of delayed fluorescence is the same as that of fluorescence but is different from that of fluorescence in that the decay time (decay time) is long, and S exists at the peak position of the emission spectrum compared with that of phosphorescence spectrum although the decay time is long₁-T₁The difference in energy is distinguished from phosphorescence.

In the present specification, when a part is referred to as "including" a certain component, unless specifically stated to the contrary, it means that the other component may be further included, and the other component is not excluded.

In the present specification, examples of the substituent are described below, but not limited thereto.

The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substituted position is not limited as long as the hydrogen atom is substituted, that is, the position at which the substituent may be substituted, and when 2 or more substituents are substituted, 2 or more substituents may be the same as or different from each other.

The term "substituted or unsubstituted" as used herein means substituted with 1 or 2 or more substituents selected from deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a carbonyl group, an ester group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boron group, a substituted or unsubstituted amine group, a substituted or unsubstituted arylphosphino group, a substituted or unsubstituted phosphinoxide group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group, or with a substituent in which 2 or more substituents among the above-exemplified substituents are linked, or do not have any substituents. For example, "a substituent in which 2 or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which 2 phenyl groups are linked.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 30. Specifically, the compound may have the following structure, but is not limited thereto.

In the amide group, the nitrogen of the amide group may be replaced by hydrogen; a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, the compound may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 30. Specifically, the compound may have the following structure, but is not limited thereto.

In the ester group, in the present specification, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, the compound may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples thereof include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methylbutyl group, 1-ethylbutyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2-dimethylheptyl group, 1-ethyl-propyl group, 1-dimethyl-propyl group, 1-, Isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 30 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the alkoxy group may be a straight chain, a branched chain or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but the number of carbon atoms is preferably 1 to 30. Specifically, it may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-neoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzyloxy, etc., but is not limited thereto.

In the present specification, the amine group may be selected from-NH₂The number of carbon atoms of the alkylamino group, the N-alkylarylamino group, the arylamine group, the N-arylheteroarylamino group, the N-alkylheteroarylamino group, and the heteroarylamino group is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include, but are not limited to, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamino group, a naphthylamino group, a biphenylamino group, an anthrylamino group, a 9-methylanthrylamino group, a diphenylamino group, an N-phenylnaphthylamino group, a ditolylamino group, an N-phenyltolylamino group, a triphenylamino group, an N-phenylbiphenylamino group, an N-phenylnaphthylamino group, an N-biphenylnaphthylamino group, an N-naphthylfluorenylamino group, an N-phenylphenanthrylamino group, an N-biphenylphenanthrylamino group, an N-phenylfluorenylamino group, and an N-biphenylfluorenylamino group.

In the present specification, the N-alkylarylamino group means an amino group in which an alkyl group and an aryl group are substituted on N of the amino group.

In the present specification, the N-arylheteroarylamino group means an amino group in which an aryl group and a heteroaryl group are substituted on the N of the amino group.

In the present specification, the N-alkylheteroarylamino group means an amino group in which an alkyl group and a heteroaryl group are substituted on N of the amino group.

In the present specification, the alkyl group in the alkylamino group, N-arylalkylamino group, alkylthio group, alkylsulfonyl group, N-alkylheteroarylamino group is the same as that exemplified above for the alkyl group. Specifically, examples of the alkylthio group include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, and an octylthio group, and examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and a butylsulfonyl group, but the alkylsulfanyl group is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples thereof include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylethen-1-yl, 2-diphenylethen-1-yl, 2-phenyl-2- (naphthyl-1-yl) ethen-1-yl, 2-bis (biphenyl-1-yl) ethen-1-yl, stilbenyl, and styryl.

In the present specification, specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.

In this specification, the boron group may be-BR₁₀₀R₁₀₁R is as defined above₁₀₀And R₁₀₁The same or different from each other, may be each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group of carbon number 3 to 30, a substituted or unsubstituted linear or branched alkyl group of carbon number 1 to 30, a substituted or unsubstituted monocyclic or polycyclic aryl group of carbon number 6 to 30, and a substituted or unsubstituted monocyclic or polycyclic heteroaryl group of carbon number 2 to 30.

In the present specification, specific examples of the phosphine oxide group include a diphenylphosphine oxide group, a dinaphthylphosphine oxide group and the like, but the phosphine oxide group is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

The number of carbon atoms in the case where the aryl group is a monocyclic aryl group is not particularly limited, but is preferably 6 to 30. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto.

The number of carbon atoms in the case where the aryl group is a polycyclic aryl group is not particularly limited, but is preferably 10 to 30. Specifically, the polycyclic aromatic group may be a naphthyl group, an anthryl group, a phenanthryl group, a triphenyl group, a pyrenyl group, a phenalenyl group, a perylenyl group, a perylene group,Examples of the group include a fluorenyl group and a fluoranthenyl group.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may be bonded to each other to form a ring.

When the fluorenyl group is substituted, the compound may be,

and the like. But is not limited thereto.

In the present specification, an "adjacent" group may refer to a substituent substituted on an atom directly connected to an atom substituted with the substituent, a substituent sterically closest to the substituent, or another substituent substituted on an atom substituted with the substituent. For example, 2 substituents substituted at the ortho (ortho) position in the phenyl ring and 2 substituents substituted on the same carbon in the aliphatic ring may be interpreted as groups "adjacent" to each other.

In the present specification, the aryl group in the aryloxy group, the arylthio group, the arylsulfonyl group, the N-arylalkylamino group, the N-arylheteroarylamino group, and the arylphosphino group is the same as the above-mentioned examples of the aryl group. Specifically, the aryloxy group includes, but is not limited to, phenoxy, p-tolyloxy, m-tolyloxy, 3, 5-dimethylphenoxy, 2,4, 6-trimethylphenoxy, p-tert-butylphenoxy, 3-biphenyloxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthracenyloxy, 2-anthracenyloxy, 9-anthracenyloxy, 1-phenanthrenyloxy, 3-phenanthrenyloxy, 9-phenanthrenyloxy, and the like, and the arylthio group includes phenylthio, 2-methylphenylthio, 4-tert-butylphenylthio, and the like, and the arylsulfonyl group includes benzylsulfonyl, p-tolylsulfonyl, and the like.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group and a substituted or unsubstituted diarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing 2 or more of the above-mentioned aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or both a monocyclic aryl group and a polycyclic aryl group. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heteroaryl group includes one or more heteroatoms other than carbon atoms, and specifically, the heteroatoms may include one or more atoms selected from O, N, Se and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,Azolyl group,Oxadiazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinylAzolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl (phenanthroline), isoquinoylExamples of the heterocyclic group include, but are not limited to, an azole group, a thiadiazole group, a phenothiazine group, and a dibenzofuran group.

In the present specification, as examples of the heteroarylamino group, there may be mentioned a substituted or unsubstituted monoheteroarylamino group, or a substituted or unsubstituted diheteroarylamino group. Heteroarylamine groups containing more than 2 of the above-mentioned heteroaryls are monocyclic heteroaryls, polycyclic heteroaryls, or may contain both monocyclic heteroaryls and polycyclic heteroaryls. For example, the heteroaryl group in the above-mentioned heteroarylamine group may be selected from the examples of the above-mentioned heteroaryl group.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamino group and the N-alkylheteroarylamino group are the same as those exemplified above for the heteroaryl group.

According to one embodiment of the present specification, the compound represented by the above chemical formula 1 has both an electron Acceptor (Acceptor) such as a triazine group and a dicarbazole group functioning as an electron Donor (Donor) in the compound, and by introducing these substituents into appropriate positions, the energy difference between the singlet state and the triplet state of the compound as a whole can be appropriately adjusted. Thereby, Thermally Activated Delayed Fluorescence (TADF) can be exhibited.

According to an embodiment of the present specification, the triplet (triplet) level of the compound represented by the above chemical formula 1 is 2.0eV or more, specifically, 2.0eV or more and 3eV or less, more specifically, 2.4eV or more and 2.9eV or less. When the triplet level satisfies the above range, an organic light-emitting element having a low driving voltage, a long life, and excellent light-emitting efficiency can be realized.

According to one embodiment of the present disclosure, the difference between the singlet (singlet) level and the triplet (triplet) level of the compound represented by the above chemical formula 1 is 0.3eV or less, specifically 0.25eV or less and 0.01eV or more, more specifically 0.2eV or less and 0.05eV or more. The difference between the singlet (singlet) level and the triplet (triplet) level is the absolute value of the singlet (singlet) level to the triplet (triplet) level. When the difference between the singlet (singlet) level and the triplet (triplet) level satisfies the above range, intramolecular orbital overlap (orbitaltoverlap) can be effectively blocked, so that the singlet and triplet states do not overlap, and the above difference can be obtained very low. Thus, reverse intersystem crossing from a triplet excited (excited) state to a singlet excited state can be achieved by thermal activation even at normal temperature, and delayed fluorescence can be displayed.

The triplet energy level and the singlet energy level can be measured by a method known in the art, but are not limited thereto.

According to an embodiment of the present specification, the chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-3.

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

In the above chemical formulas 1-1 to 1-3, R1 to R14 are the same as defined in the above chemical formula 1.

According to an embodiment of the present disclosure, in the chemical formula 1, R1 to R14 are hydrogen.

According to an embodiment of the present specification, the above chemical formula 1 is represented by any one of the following chemical formulas 1-4 to 1-6.

[ chemical formulas 1 to 4]

[ chemical formulas 1 to 5]

[ chemical formulas 1 to 6]

According to an embodiment of the present disclosure, the chemical formula 1 is selected from the following compounds.

According to one embodiment of the present specification, there is provided an organic light-emitting element including a delayed fluorescence material composed of the compound represented by chemical formula 1.

According to one embodiment of the present specification, there is provided an organic light-emitting element including: the organic el device includes a first electrode, a second electrode provided so as to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers include the delayed fluorescent material.

In the present specification, when a member is referred to as being "on" another member, it includes not only a case where the member is in contact with the another member but also a case where the another member is present between the two members.

According to one embodiment of the present description, the organic layer of the organic light-emitting device described in the present description may have a single-layer structure, or may have a multilayer structure in which two or more organic layers are stacked. For example, the organic light-emitting element of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like as an organic layer. However, the structure of the organic light emitting element is not limited thereto, and fewer or more organic layers may be included.

For example, the structure of the organic light-emitting element in the present specification may have the same structure as that shown in fig. 1, but is not limited thereto.

Fig. 1 illustrates a structure of an organic light emitting element 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20. Fig. 1 illustrates an exemplary structure of an organic light emitting device according to an embodiment of the present disclosure, and may further include another organic layer.

According to one embodiment of the present disclosure, the organic layer includes a light emitting layer, and the light emitting layer includes the delayed fluorescence material.

According to one embodiment of the present disclosure, the organic layer includes a light emitting layer, and the light emitting layer includes the delayed fluorescence material as a dopant of the light emitting layer.

According to one embodiment of the present disclosure, the light-emitting substance of the light-emitting layer is a substance capable of receiving holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combining them to emit light in a visible light region, and the light-emitting layer contains the delayed fluorescent material as a dopant of the light-emitting layer, and at least one of excited singlet energy and excited triplet energy has a higher value than that of the light-emitting material of the delayed fluorescent material, and may contain an organic compound having a hole-transporting ability and an electron-transporting ability, preventing a wavelength of light emission from increasing, and having a high glass transition temperature as a host.

According to one embodiment of the present disclosure, the organic layer includes a light emitting layer including a dopant and a host in a weight ratio of 1:99 to 40: 60.

According to one embodiment of the present disclosure, the organic layer includes a light emitting layer including a dopant and a host including the delayed fluorescent material in a weight ratio of 1:99 to 40: 60.

The organic light emitting device of the present specification can be manufactured by using a material and a method known in the art, except that the light emitting layer contains the delayed fluorescence material of the present specification, that is, the delayed luminescence material composed of the compound represented by the above chemical formula 1.

When the organic light-emitting element includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

For example, the organic light-emitting element of the present specification can be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. This can be produced as follows: the organic el device is manufactured by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a Physical Vapor Deposition (PVD) method such as a sputtering method or an electron beam evaporation (e-beam evaporation) method to form a first electrode, then forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer on the first electrode, and then depositing a substance that can be used as a second electrode on the organic layer. In addition to this method, the second electrode, the organic layer, and the first electrode may be sequentially deposited on the substrate to manufacture the organic light-emitting element. In addition, the heterocyclic compound represented by the above chemical formula 1 may be used not only for forming an organic layer by a vacuum evaporation method but also for forming an organic layer by a solution coating method in the production of an organic light-emitting element. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

According to an embodiment of the present disclosure, the first electrode is an anode, and the second electrode is a cathode.

In another embodiment of the present disclosure, the first electrode is a cathode, and the second electrode is an anode.

The anode material is preferably a material having a large work function in order to smoothly inject holes into the organic layer. Specific examples of the anode material which can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, and alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); such as ZnO, Al or SnO₂A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole, polyaniline, and other conductive polymers, but the present invention is not limited thereto.

The cathode material is preferably a material having a small work function in order to easily inject electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; such as LiF/Al or LiO₂Multilayer structure materials such as/Al, Mg/Ag, etc., but not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and the following compounds are preferable as the hole injection substance: has an ability to transport holes, has a hole injection effect from the anode, has an excellent hole injection effect with respect to the light-emitting layer or the light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or the electron injection material, and has excellent thin film-forming ability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injecting substance is between the work function of the anode substance and the HOMO of the surrounding organic layer. Specific examples of the hole injecting substance include, but are not limited to, metalloporphyrin (porphyrin), oligothiophene, arylamine-based organic substances, hexanitrile-hexaazatriphenylene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer, and the hole transport material is a material that can receive holes from the anode or the hole injection layer and transport the holes to the light-emitting layer, and is suitable for a material having a high hole mobility. Specific examples thereof include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers in which a conjugated portion and a non-conjugated portion are present simultaneously.

The electron transporting layer is a layer which receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and the electron transporting material is a material which can inject electrons from the cathode well and transfer the electrons to the light emitting layer, and a material having a large electron mobility is a material which is combinedAnd (6) appropriately. Specific examples thereof include Al complexes of 8-hydroxyquinoline and Al complexes containing Alq₃The complex of (a), an organic radical compound, a hydroxyflavone-metal complex, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in the art. Examples of suitable cathode substances are, in particular, the customary substances having a low work function and accompanied by an aluminum or silver layer. In particular cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum or silver layer.

The electron injection layer is a layer for injecting electrons from the electrode, and is preferably a compound of: has an ability to transport electrons, an electron injection effect from a cathode, an excellent electron injection effect with respect to a light-emitting layer or a light-emitting material, prevents excitons generated in the light-emitting layer from migrating to a hole-injecting layer, and is excellent in thin-film formability. Specifically, there are fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like,Azole,Oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex include lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), and gallium tris (8-quinolinolato), bis (10-hydroxybenzo [ h ] quinoline) beryllium, bis (10-hydroxybenzo [ h ] quinoline) zinc, bis (2-methyl-8-quinoline) gallium chloride, bis (2-methyl-8-quinoline) (o-cresol) gallium, bis (2-methyl-8-quinoline) (1-naphthol) aluminum, bis (2-methyl-8-quinoline) (2-naphthol) gallium, and the like, but are not limited thereto.

The organic light emitting element according to the present specification may be a top emission type, a bottom emission type, or a bidirectional emission type, depending on the material used.

According to an embodiment of the present specification, the delayed fluorescent material may be included in an organic solar cell or an organic transistor in addition to the organic light emitting element.

Modes for carrying out the invention

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present description may be modified into various forms, and the scope of the description should not be construed as being limited to the embodiments described in detail below. The embodiments of the present description are provided to more fully describe the present description to those skilled in the art.

Production example 1 production of Compound 1

1) Production of intermediate 1-1

5-bromo-2-fluorophenylcyanide (5-bromo-2-fluoronitrile) (10g,50.27mmol), bis (pinacolato) diboron (15.32g, 60.32mmol), [1,1 '-bis (diphenylphosphino) ferrocene ] dichloropalladium (II) ([1,1' -bis (phenylphosphino) ferrocene ] dichlorocene (II)) (1.46g, 2.01mmol) and potassium acetate (potassium acetate) (9.87g, 100.54mmol) were completely dissolved in 100ml Dimethylformamide (Dimethylformamide), and then stirred at elevated temperature until reflux. The reaction was terminated 12 hours after the start of reflux, the temperature was lowered to normal temperature, the reaction mixture was concentrated under reduced pressure, and the product was purified by column chromatography to give 9.81g of intermediate 1-1.

MS[M+H]⁺＝248

2) Production of intermediate 1-2

The above intermediate 1-1(9.81g, 39.70mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) (10.6g, 39.70mmol) and tetrakis (triphenylphosphine) palladium (0) (Tetrakis (triphenylphoshine) palladium (0)) (0.46g, 0.40mmol) were added to Tetrahydrofuran (Tetrahydrofuran)60ml, mixed with an aqueous solution of potassium carbonate (16.46g, 119.1mmol) and stirred, and the temperature was raised until reflux. The reaction was terminated 6 hours after the start of reflux, the temperature was lowered to normal temperature, the reaction mixture was concentrated under reduced pressure, and the product was purified by column chromatography to obtain 17.26g of intermediate 1-2.

MS[M+H]+＝353

3) Production of Compound 1

The above intermediate 1-2(17.26g, 49.02mmol), 9-phenyl-9H,9'H-3,3' -dicarbazole (9-phenyl-9H,9'H-3,3' -dicarbazole) (20.0g, 49.02mmol) and cesium carbonate (cecum carbonate) (47.91g, 147.06mmol) were added to 120ml of Dimethylformamide (dimethyl formamide), the temperature was raised, and stirring was performed under reflux conditions. After 5 hours, the reaction was terminated, the temperature was lowered to normal temperature, and after concentration under reduced pressure, 27.94g (yield) 77%) of compound 1 was produced by column purification.

MS[M+H]⁺＝741

The physical properties of compound 1 produced according to production example 1 are as follows.

FIG. 2 is a graph showing NMR data of Compound 1, which was measured using Unity Inova from Varian Technology.

FIG. 3 shows a UV-vis absorption spectrum of Compound 1, which is 1X 10 in an amount of Compound 1, a photoluminescence spectrum in a solid state, and a photoluminescence spectrum in a Low-Temperature (Low-Temperature) state, wherein the UV-vis absorption spectrum is measured by V-730 of JASCO corporation, the absorption spectrum is 200nm to 800nm, and HPLC-grade THF is used as a solvent^-5And M. Photoluminescence spectrum in solid state was measured by LS-55 of Perkin Elmer, excitation (excitation) wavelength of 370nm with an emission spectrum of 400nm to 660nm, HPLC grade THF was used as a solvent, and the content of the above compound 1 was 1X 10^-5And M. Photoluminescence spectrum in a Low-Temperature (Low-Temperature) state was measured with LS-55 from Perkin Elmer, an excitation wavelength of 360nm was 400nm to 700nm, HPLC-grade THF was used as a solvent, and the content of the above-mentioned compound 1 was 1X 10^-5M, measured under liquid nitrogen conditions.

In FIG. 2, the emission peak wavelength of the solid phase is 488nm, and the emission peak wavelength of the Low-Temperature (Low-Temperature) phase is 499 nm.

The physical properties of compound 1 measured in fig. 2 are shown in table 1 below.

[ Table 1]

Fig. 4 is a cyclic voltammetry (cyclic voltammetry) chart of compound 1 according to an embodiment of the present description. The data were measured using Iviumstat from Ivium Tech, and HPLC grade MC was used as the solvent. The ionization potential, electron affinity, and band gap of compound 1 obtained by cyclic voltammetry (cyclic voltammetry) are shown in table 2 below.

[ Table 2]

	Ionization potential (eV)	Electron affinity (eV)	Band gap (CV)
				Compound 1	-5.81	-3.44	2.37

Production example 2 production of Compound 2

1) Production of intermediate 2-1

9.07g of intermediate 2-1 was produced by the same method except that 2-bromo-5-fluorobenzonitrile (2-bromo-5-fluorobenzonitrile) (10g,50.27mmol) was used in place of 5-bromo-2-fluorobenzonitrile (5-bromo-2-fluorobenzonitrile) in the production of 1) intermediate 1-1 of production example 1.

MS[M+H]⁺＝248

2) Production of intermediate 2-2

Production was carried out in the same manner as in production example 1, except that 2) of intermediate 1-2 was used in place of intermediate 1-1, intermediate 2-1(9.07, 36.70mmol) was used to produce 10.21g of intermediate 2-2.

MS[M+H]⁺＝353

3) Production of Compound 2

Compound 2 was produced in the same manner as in 3) of production example 1 except that intermediate 2-2(10.21g, 28.99mmol) was used instead of intermediate 1-2 in the production of compound 1, thereby producing 16.62g (yield 76%).

MS[M+H]⁺＝741

The physical properties of compound 2 produced in production example 2 are as follows.

FIG. 5 is a graph showing NMR data of Compound 2, which was measured using Unity Inova from Varian Technology.

FIG. 6 shows a UV-vis absorption spectrum of Compound 2, which is 1X 10 in terms of the content of Compound 2, a photoluminescence spectrum in a solid state, and a photoluminescence spectrum in a Low-Temperature (Low-Temperature) state, wherein the UV-vis absorption spectrum is measured by V-730 of JASCO corporation, the absorption spectrum is 200nm to 800nm, and HPLC-grade THF is used as a solvent^-5And M. Photoluminescence spectrum in solid state was measured by LS-55 from Perkin Elmer, 420nm to 750nm as excitation wavelength, HPLC grade THF was used as solvent, and the content of the above compound 2 was 1X 10^-5And M. Photoluminescence spectrum in a Low-Temperature (Low-Temperature) state was measured using L from Perkin ElmerS-55, an excitation wavelength of 350nm is 400nm to 670nm, HPLC-grade THF is used as a solvent, and the content of the compound 2 is 1X 10^-5M, measured under liquid nitrogen conditions.

In FIG. 6, the emission peak wavelength in the solid state is 465nm, and the emission peak wavelength in the Low-Temperature (Low-Temperature) state is 483 nm.

The physical properties of compound 2 measured in fig. 6 are shown in table 3 below.

[ Table 3]

Fig. 5 is a cyclic voltammetry (cyclic voltammetry) graph of compound 2 according to an embodiment of the present description. The data were measured using Iviumstat from Ivium Tech, and HPLC grade MC was used as the solvent. The ionization potential, electron affinity, and band gap of compound 2 obtained by the cyclic voltammetry (cyclic voltammetry) are shown in table 4 below.

[ Table 4]

	Ionization potential (eV)	Electron affinity (eV)	Band gap (CV)
				Compound 2	-5.76	-3.47	2.29

Production example 3 production of Compound 6

1) Production of intermediate 3-1

9.31g of intermediate 3-1 was produced in the same manner as in 1) of production example 1 except that 3-bromo-2-fluorobenzonitrile (3-bromo-2-fluorobenzonitrile) (10g,50.27mmol) was used in place of 5-bromo-2-fluorobenzonitrile (5-bromo-2-fluorobenzonitrile).

MS[M+H]⁺＝248

2) Production of intermediate 3-2

Production was carried out in the same manner as in 2) of production example 1 except that the intermediate 3-1(9.31, 37.67mmol) was used in place of the intermediate 1-1 in the production of the intermediate 1-2, thereby producing 10.53g of the intermediate 3-2.

MS[M+H]⁺＝353

3) Production of Compound 6

17.05g (yield 77%) of compound 6 was produced by the same method except that the intermediate 3-2(10.53g, 29.91mmol) was used instead of the intermediate 1-2 in the production of compound 1 of 3) of production example 1.

MS[M+H]⁺＝741

[ example 1-1]

Will be provided withThe glass substrate coated with ITO (indium tin oxide) is put in distilled water in which a detergent is dissolved, and washed by ultrasonic waves. In this case, the detergent used was a product of fisher (fischer Co.) and the distilled water used was distilled water filtered twice with a Filter (Filter) manufactured by Millipore Co. The ITO was washed for 30 minutes and then twice with distilled water to perform ultrasonic washing for 10 minutes. Washing the precipitate with distilled waterAfter that, the substrate was ultrasonically washed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and then conveyed to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transported to a vacuum evaporator.

On the ITO transparent electrode thus prepared, toThe following N1, N1'- ([1,1' -biphenyl ]) was thermally vacuum-deposited to a thickness of (1)]-4,4' -diyl) bis (N1-phenyl N4, N4-di-m-tolylbenzene-1, 4-diamine) (N1, N1' - ([1,1' -biphenyl)]-4,4'-diyl)bis(N1-phenyl-N4,N4-di-m-tolylbenzene-1,4-dia mine))[DNTPD]Thereby forming a hole injection layer. On the hole injection layer, the following N4, N4, N4', N4' -tetrakis ([1,1' -biphenyl ] were sequentially formed]-4-yl) - [1,1' -biphenyl]-4,4 '-diamine (N4, N4, N4', N4'-tetra ([1,1' -biphenyl)]-4-yl)-[1,1'-biphenyl]-4,4'-diamine)[BPBPA]To be provided withAnd 9,9-dimethyl-10- (9-phenyl-9H-carbazol-3-yl) -9,10-dihydroacridine (9,9-dimethyl-10- (9-phenyl-9H-carbazol-3-yl) -9,10-dihydroacridine) [ PCZAC]To be provided withVacuum evaporation is performed to form a hole transport layer. Then, on the hole transport layer, the film thicknessThe following 9- (3'- (4,6-diphenyl-1,3,5-triazin-2-yl) - [1,1' -biphenyl ] is added]-3-yl) -9H-carbazole (9- (3'- (4,6-diphenyl-1,3,5-triazin-2-yl) - [1,1' -biphenyl ]]-3-yl)-9H-carbazole)[DC_Z]And the compound 1 was vacuum-evaporated at a weight ratio of 100:3 to form a light-emitting layer.

On the light-emitting layer, the following 2,8-bis (4,6-diphenyl-1,3,5-triazin-2-yl) dibenzo [ b, d]Furan (2,8-bis (4,6-diphenyl-1,3,5-triazin-2-yl) dibezo [ b, d]furan)[DBFTrz]And 2- (4- (9, 10-bis (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d]Imidazole (2- (4- (9,10-di (n-aphthalen-2-yl) a)nthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole)[ZAD N]In turn withThe thickness of (2) forms an electron transport layer. On the electron transport layer, lithium fluoride (LiF) is sequentially addedThickness of aluminum andthe electron injection layer and the cathode are formed by vapor deposition.

In the above process, the evaporation rate of the organic material is maintained at 0.4-0.4Sec, maintenance of lithium fluoride at the cathodeEvaporation Rate,/sec, aluminum maintenanceA vapor deposition rate of/sec, and a degree of vacuum maintained at 1X 10 during vapor deposition^-7To 5X 10^-8And (4) supporting to manufacture the organic light-emitting element.

[ examples 1-2]

An organic light-emitting element was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, DCz was vacuum-deposited with the compound 1 at a weight ratio of 20: 1.

[ examples 1 to 3]

An organic light-emitting element was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, DCz was vacuum-deposited with the compound 1 at a weight ratio of 10: 1.

[ examples 1 to 4]

An organic light-emitting element was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, DCz was vacuum-deposited with the compound 1 at a weight ratio of 5: 1.

[ examples 1 to 5]

An organic light-emitting device was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, the compound 2 was used instead of the compound 1.

[ examples 1 to 6]

Organic light-emitting elements were produced in the same manner as in experimental examples 1 to 5, except that in experimental examples 1 to 5, DCz and the compound 2 were vacuum-deposited at a weight ratio of 20: 1.

[ examples 1 to 7]

Organic light-emitting elements were produced in the same manner as in experimental examples 1 to 5, except that in experimental examples 1 to 5, DCz and the compound 2 were vacuum-deposited at a weight ratio of 10: 1.

[ examples 1 to 8]

Organic light-emitting elements were produced in the same manner as in experimental examples 1 to 5, except that in experimental examples 1 to 5, DCz and the compound 2 were vacuum-deposited at a weight ratio of 5: 1.

[ examples 1 to 9]

An organic light-emitting device was produced in the same manner as in experimental example 1-1, except that the compound 6 was used instead of the compound 1 in experimental example 1-1.

Comparative examples 1 to 1

An organic light-emitting element was produced in the same manner as in experimental examples 1 to 4, except that in experimental examples 1 to 4, the following D1 was used instead of compound 1.

Comparative examples 1 and 2

An organic light-emitting element was produced in the same manner as in experimental examples 1 to 4, except that in experimental examples 1 to 4, the following D2 was used instead of compound 1.

Comparative examples 1 to 3

An organic light-emitting element was produced in the same manner as in experimental examples 1 to 4, except that in experimental examples 1 to 4, the following D3 was used instead of compound 1.

Current-voltage-luminance (IVL), color Coordinates (CIE), Quantum Efficiency (QE), Luminous Efficiency (LE), and current efficiency (J) characteristics of the organic light emitting elements manufactured in examples 1-1 to 1-9 and comparative examples 1-1 to 1-3 were measured using a PR-655IVL instrument of Photo Research, and the results are shown in tables 5 and 6 below.

[ Table 5]

[ Table 6]

As shown in the above tables 5 and 6, in examples 1-1 to 1-9, which belong to an organic light emitting element including chemical formula 1 according to an embodiment of the present specification as a delayed fluorescent material, triazinyl and dicarbazole are connected centering on phenylene group to which CN is bonded, and the organic light emitting element including the same has advantages of low driving voltage, low current density, higher luminance, and excellent quantum efficiency, light emitting efficiency, and current efficiency, as compared to comparative examples 1-1 to 1-3, which belong to organic light emitting elements including compounds of D1 to D3.