KR20230046493A - Organic light emitting device, composition for organic layer of organic light emitting device and manufacturing method of organic light emitting device - Google Patents

Abstract

The present specification, as an organic light emitting element comprising a first electrode, a second electrode, and an organic material layer of one or more layers equipped between the first electrode and the second electrode, relates to the organic light emitting element comprising a heterocyclic compound wherein a first layer or more among the organic material layer is represented by chemical formula 1 and a heterocyclic compound represented by chemical formula 2; a composition for an organic material layer of the organic light emitting element; and a manufacturing method of the organic light emitting element. Therefore, the present invention is capable of improving a lifespan characteristic of the element.

Description

Organic light emitting device, composition for organic material layer of organic light emitting device, and manufacturing method of organic light emitting device

The present specification relates to an organic light emitting device, a composition for an organic material layer of the organic light emitting device, and a method for manufacturing the organic light emitting device.

The electroluminescent device is a type of self-luminous display device, and has advantages such as a wide viewing angle, excellent contrast, and fast response speed.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes are combined in the organic thin film to form a pair, and then emit light while disappearing. The organic thin film may be composed of a single layer or multiple layers as needed.

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of constituting the light emitting layer by itself may be used, or a compound capable of serving as a host or dopant of the host-dopant type light emitting layer may be used. In addition, as a material for the organic thin film, a compound capable of performing functions such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, lifespan or efficiency of organic light emitting devices, the development of materials for organic thin films is continuously required.

U.S. Patent No. 4,356,429

The present invention is to provide an organic light emitting device, a composition for an organic material layer of the organic light emitting device, and a method for manufacturing the organic light emitting device.

An exemplary embodiment of the present application is an organic light emitting device including a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode,

At least one layer of the organic material layer provides an organic light emitting device comprising a heterocyclic compound represented by Formula 1 below and a heterocyclic compound represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X1 to X3 are the same as or different from each other, and each independently N; or CRc, at least one is N;

A is a substituted or unsubstituted C6 to C20 arylene group; Or a substituted or unsubstituted C2 to C20 heteroarylene group,

R1 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; SiRR'R”; or -P(=0)RR';

L1 to L3 are the same as or different from each other and are each independently a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,

Ar1 and Ar2 are the same as or different from each other and are each independently a substituted or unsubstituted C1 to C60 alkyl group; Or a substituted or unsubstituted C6 to C60 aryl group;

Ar3 is a substituted or unsubstituted carbazole group; A substituted or unsubstituted C10 to C60 aryl group; Or a C2 to C60 heteroaryl group containing O or S as a substituted or unsubstituted heterogeneous element,

Wherein R, R', and R" are the same as or different from each other and each independently represents a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 A heteroaryl group of

Wherein Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group;

a1 to a3 are the same as or different from each other and each independently represent an integer of 0 to 4, and when a1 to a3 are 2 or more, the substituents in parentheses are the same as or different from each other,

Formula 1 is a bond of the following Structural Formula A to Structural Formula C,

[Structural Formula A]

[Structural Formula B]

[Structural Formula C]

In the structural formulas A to C,

는 구조식 A 내지 C가 각각 결합하는 위치이고,

is a position at which structural formulas A to C are bonded, respectively,

the structural formula A and the structural formula B; Structural Formula C above; Alternatively, the deuterium content of the structural formulas A to C is 50% to 100%.

In addition, another exemplary embodiment of the present application provides a composition for an organic layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 above.

Finally, an exemplary embodiment of the present application includes preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the organic material layer includes forming one or more organic material layers using the composition for an organic material layer according to the present application. A manufacturing method is provided.

The heterocyclic compound according to an exemplary embodiment of the present application may be used as a material for an organic material layer of an organic light emitting device. The heterocyclic compound may be used as a material for a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or a charge generating layer in an organic light emitting device. In particular, the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be simultaneously used as materials for a light emitting layer of an organic light emitting device. In addition, when the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 are simultaneously used in an organic light emitting device, the driving voltage of the device is lowered, the light efficiency is improved, and the thermal stability of the compound improves the efficiency of the device. life characteristics can be improved.

In particular, the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be simultaneously used as materials for a light emitting layer of an organic light emitting device. In this case, it is possible to lower the driving voltage of the device, improve the light efficiency, and particularly improve the lifespan characteristics of the device due to the thermal stability of the compound.

Moreover, the compound of Formula 1 corresponds to a compound substituted with deuterium whose atomic weight is twice that of hydrogen, and has an effect of stabilizing radicals that may be generated when intermolecular electron transport occurs. In addition, since the bond dissociation energy of carbon and deuterium is greater than the bond dissociation energy of carbon and hydrogen, the thermal stability of the molecule is high, and life characteristics can be improved. Therefore, when Formula 1 and Formula 2 having specific substituent characteristics are combined, the higher the ratio of Formula 1, the higher the content of deuterium in the device, thereby maximizing its characteristics.

1 to 3 are diagrams schematically illustrating a stacked structure of an organic light emitting device according to an exemplary embodiment of the present application.
4 is a diagram showing HOMO Electronic Distribution, LUMO Electronic Distribution, and SOMO Electronic Distribution according to Chemical Formula 1 of the present invention, respectively.

Hereinafter, this application will be described in detail.

In the present invention, "when no substituent is shown in the chemical formula or compound structure" means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( ² H, Deuterium) and tritium ( ³ H, Tritium) are isotopes of hydrogen, some hydrogen atoms may be deuterium or tritium.

In one embodiment of the present invention, "when no substituent is shown in the chemical formula or compound structure" may mean that all positions where the substituent can occur are hydrogen, deuterium, or tritium. That is, deuterium and tritium are isotopes of hydrogen, and some hydrogen atoms may be isotopes of deuterium and tritium, in which case the content of deuterium or tritium may be 0% to 100%.

In one embodiment of the present invention, in “when no substituent is indicated in the chemical formula or compound structure”, “the content of deuterium is 0%”, “the content of tritium is 0%”, “the content of hydrogen is 100 ”, “All substituents are hydrogen”, etc., hydrogen, deuterium, and tritium may be mixed and used in a compound unless deuterium and tritium are explicitly excluded.

In one embodiment of the present invention, deuterium is one of the isotopes of hydrogen and is an element having a deuteron composed of one proton and one neutron as an atomic nucleus, hydrogen- It can be expressed as 2, and the element symbol can also be written as D or ² H. Similarly, the element symbol for tritium can also be written as T or ^3H .

In one embodiment of the present invention, isotopes, which mean atoms having the same atomic number (Z) but different mass numbers (A), have the same number of protons, but have neutrons. It can also be interpreted as an element with a different number of neutrons.

In one embodiment of the present invention, the meaning of the content T% of a specific substituent is when the total number of substituents that a base compound can have is defined as T1, and the number of specific substituents among them is defined as T2. T2 It can be defined as /T1×100 = T%.

로 표시되는 페닐기에 있어서 중수소의 함량 20%라는 것은 페닐기가 가질 수 있는 치환기의 총 개수는 5(식 중 T1)개이고, 그 중 중수소의 개수가 1(식 중 T2)인 경우를 의미할 수 있다. 즉, 페닐기에 있어서 중수소의 함량 20%라는 것인 하기 구조식으로 표시될 수 있다.That is, in one example,

In the phenyl group represented by 20% of the deuterium content may mean that the total number of substituents that the phenyl group may have is 5 (T1 in the formula), and the number of deuterium is 1 (T2 in the formula) . That is, it can be represented by the following structural formula that the content of deuterium in the phenyl group is 20%.

In addition, in an exemplary embodiment of the present application, in the case of "a phenyl group having a deuterium content of 0%", it may mean a phenyl group without deuterium atoms, that is, having 5 hydrogen atoms.

In the present specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, the position where the substituent can be substituted, When two or more substituents are substituted, two or more substituents may be the same as or different from each other.

In the present specification, "substituted or unsubstituted" deuterium; halogen; cyano group; C1 to C60 straight or branched chain alkyl; C2 to C60 straight or branched alkenyl; C2 to C60 straight or branched alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; -SiRR'R"; -P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; and C2 to C60 monocyclic or polycyclic heteroarylamine selected from the group consisting of It means substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent in which two or more substituents selected from the substituents exemplified above are connected.

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

In the present specification, the alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically, 1 to 20. Specific examples 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-methyl-butyl group, 1- Ethyl-butyl 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, 3,3-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, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited thereto.

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40, and more specifically, 2 to 20. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1 -butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but is not limited thereto.

In the present specification, the alkynyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20.

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be, but is not limited thereto.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic group having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a cycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may also be another type of ring group, such as a heterocycloalkyl group, an aryl group, a heteroaryl group, and the like. The number of carbon atoms in the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 ,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, etc., but are not limited thereto.

In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a heterocycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may also be another type of ring group, such as a cycloalkyl group, an aryl group, a heteroaryl group, and the like. The heterocycloalkyl group may have 2 to 60, specifically 2 to 40, and more specifically 3 to 20 carbon atoms.

In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted with other substituents. Here, the polycyclic means a group in which an aryl group is directly connected or condensed with another cyclic group. Here, the other ring group may be an aryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, and the like. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, and a pyrene group. Nyl group, tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, condensed ring groups thereof and the like, but is not limited thereto.

In the present specification, the phosphine oxide group is represented by -P(=O)R101R102, R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specifically, it may be substituted with an aryl group, and the above-described examples may be applied to the aryl group. For example, the phosphine oxide group includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, the silyl group is a substituent that includes Si and the Si atom is directly connected as a radical, and is represented by -SiR104R105R106, R104 to R106 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. It is not limited.

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

When the fluorenyl group is substituted, it may be of the following structural formula, but is not limited thereto.

In the present specification, the heteroaryl group includes S, O, Se, N or Si as a hetero atom, and includes a monocyclic or polycyclic group having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, and the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40, and more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, and a thiazolyl group. group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , thiazinyl group, dioxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolilyl group, naphthyridyl group, acridinyl group, phenanthridi Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazaindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, A phenoxazinyl group, a phenanthridyl group, an imidazopyridinyl group, a thienyl group, an indolo[2,3-a]carbazolyl group, an indolo[2,3-b]carbazolyl group, an indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenantrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthyridinyl group, phenanthrolinyl group, Benzo [c] [1,2,5] thiadiazolyl group, 5,10-dihydrodibenzo [b, e] [1,4] azasilinyl group, pyrazolo [1,5-c] quinazolinyl group , pyrido [1,2-b] indazolyl group, pyrido [1,2-a] imidazo [1,2-e] indolinyl group, 5,11-dihydroindeno [1,2-b ] carbazolyl group and the like, but is not limited thereto.

In the present specification, the amine group is a monoalkylamine group; monoarylamine group; Monoheteroarylamine group; -NH ₂ ; Dialkylamine group; Diaryl amine group; Diheteroarylamine group; an alkyl arylamine group; Alkylheteroarylamine group; And it may be selected from the group consisting of an arylheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, a 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluorene Examples include a ylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but are not limited thereto.

In the present specification, the arylene group means that the aryl group has two bonding sites, that is, a divalent group. The description of the aryl group described above can be applied except that each is a divalent group. In addition, the heteroarylene group means a heteroaryl group having two bonding sites, that is, a divalent group. The above description of the heteroaryl group may be applied except that each is a divalent group.

As used herein, "adjacent" refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. can For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as “adjacent” to each other.

An exemplary embodiment of the present application is an organic light emitting device including a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers is represented by Chemical Formula 1 It provides an organic light emitting device comprising a heterocyclic compound represented by Formula 2 and a heterocyclic compound represented by Chemical Formula 2.

In one embodiment of the present application, a group not represented by a substituent; Alternatively, all groups represented by hydrogen may mean those that can be substituted with heavy hydrogen. That is, in an exemplary embodiment of the present application, hydrogen; Alternatively, deuterium may represent a state in which each other is substitutable.

In an exemplary embodiment of the present application, R1 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; SiRR'R”; or -P(=0)RR'.

In another exemplary embodiment, R1 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; SiRR'R”; or -P(=0)RR'.

In another exemplary embodiment, R1 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1 to C40 alkyl group; A substituted or unsubstituted C6 to C40 aryl group; A substituted or unsubstituted C2 to C40 heteroaryl group; SiRR'R”; or -P(=0)RR'.

In another exemplary embodiment, R1 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; C1 to C40 alkyl group; C6 to C40 aryl group; C2 to C40 heteroaryl group; SiRR'R”; or -P(=0)RR'.

In another exemplary embodiment, R1 to R14 are the same as or different from each other, and each independently hydrogen; or deuterium.

In an exemplary embodiment of the present application, L1 and L2 are the same as or different from each other and are each independently a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or it may be a substituted or unsubstituted C2 to C60 heteroarylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other and each independently, a direct bond; A substituted or unsubstituted C6 to C40 arylene group; Or it may be a substituted or unsubstituted C2 to C40 heteroarylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other and each independently, a direct bond; A substituted or unsubstituted C6 to C20 arylene group; Or it may be a substituted or unsubstituted C2 to C20 heteroarylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other and each independently, a direct bond; Or it may be a substituted or unsubstituted C6 to C20 arylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other and each independently, a direct bond; Or it may be a C6 to C20 arylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other and each independently, a direct bond; C6 to C10 monocyclic arylene group; or a C10 to C20 polycyclic arylene group;

In another exemplary embodiment, L1 and L2 are the same as or different from each other and each independently, a direct bond; A substituted or unsubstituted phenylene group; Or it may be a substituted or unsubstituted biphenylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other and each independently, a direct bond; phenylene group; or a biphenylene group.

In an exemplary embodiment of the present application, Ar1 and Ar2 are the same as or different from each other and each independently a substituted or unsubstituted C1 to C60 alkyl group; Or it may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other and each independently a substituted or unsubstituted C1 to C40 alkyl group; Or it may be a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, Ar1 and Ar2 may be the same as or different from each other and each independently represent a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, Ar1 and Ar2 may be the same as or different from each other and each independently represent a substituted or unsubstituted C6 to C20 aryl group.

In another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other and each independently may be a C6 to C20 aryl group unsubstituted or substituted with a C1 to C10 alkyl group.

In another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other and each independently represent a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted triphenylenyl group; Or it may be a substituted or unsubstituted dimethylfluorenyl group.

In another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other and each independently, a phenyl group; biphenyl group; terphenyl group; triphenylenyl group; Or it may be a dimethyl fluorenyl group.

In an exemplary embodiment of the present application, Formula 1 may be represented by a combination of Structural Formulas A to C below.

[Structural Formula A]

[Structural Formula B]

[Structural Formula C]

In the structural formulas A to C,

는 구조식 A 내지 C가 각각 결합하는 위치이고,

is a position at which structural formulas A to C are bonded, respectively,

the structural formula A and the structural formula B; Structural Formula C above; Alternatively, the deuterium content of the structural formulas A to C is 50% to 100%.

The deuterium content of Structural Formulas A to C may mean the total amount of deuterium in the structures represented by Structural Formulas A to C.

In an exemplary embodiment of the present application, the deuterium content of Structural Formula A may be 0% to 100%.

In another embodiment, the deuterium content of structural formula A is 0% to 100%, 20% to 100%, 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100% , 70% to 100%, and may be 0% or 100%.

In an exemplary embodiment of the present application, the deuterium content of Structural Formula B may be 0% to 100%.

In another exemplary embodiment, the deuterium content of structural formula B is 0% to 100%, 20% to 100%, 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100% , 70% to 100%, and may be 0% or 100%.

In an exemplary embodiment of the present application, the deuterium content of Structural Formula C may be 0% to 100%.

In another exemplary embodiment, the deuterium content of structural formula C is 0% to 100%, 20% to 100%, 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100% , 70% to 100%, and may be 0% or 100%.

In one embodiment of the present application, the structural formula A and the structural formula B; Structural Formula C above; Alternatively, the deuterium content of Structural Formulas A to C may be 100%.

In an exemplary embodiment of the present application, the deuterium content of the structural formula A and the structural formula B may be 50% to 100%, and the deuterium content of the structural formula C may be 0%.

In another exemplary embodiment, the deuterium content of the structural formula A and the structural formula B may be 60% to 100%, and the deuterium content of the structural formula C may be 0%.

In another exemplary embodiment, the deuterium content of the structural formula A and the structural formula B may be 70% to 100%, and the deuterium content of the structural formula C may be 0%.

In another exemplary embodiment, the deuterium content of the structural formula A and the structural formula B may be 80% to 100%, and the deuterium content of the structural formula C may be 0%.

In another exemplary embodiment, the deuterium content of the structural formula A and the structural formula B may be 100%, and the deuterium content of the structural formula C may be 0%.

In Chemical Formula 1 of the present application, the LUMO (Lowest Unoccupied Molecular Orbital) electron cloud is distributed in Structural Formula A and Structural Formula B, and the HOMO (Highest Occupied Molecular Orbital) electron cloud is distributed in Structural Formula C. Therefore, the driving voltage tends to decrease as the parts of structural formula A and structural formula B serving as LUMO receive electrons better. When Structural Formulas A and B are substituted with deuterium as described above, the number of neutrons in the nucleus is greater than that of hydrogen, so that electrons can be accepted more stably, so the driving voltage is improved.

In addition, when intermolecular electron transport occurs, radicals may be generated in structural formula A and structural formula B, which serve to receive electrons. The more stable the molecule in which the radical is generated, the longer the lifetime. . SOMO (Singly Occupied Molecular Orbital) electron clouds of Chemical Formula 1 with radical anions are distributed in structural formula A and structural formula B parts. When the part with the SOMO electron cloud is replaced with deuterium, the number of neutrons in the nucleus increases compared to that of hydrogen, thereby increasing the stability of the radical anion.

4 is a diagram showing HOMO electronic distribution, LUMO electronic distribution, and SOMO electronic distribution according to Formula 1 of the present invention, respectively.

In an exemplary embodiment of the present application, the deuterium content of Structural Formula C may be 50% to 100%, and the deuterium content of Structural Formulas A and B may be 0%.

In another exemplary embodiment, the deuterium content of Structural Formula C may be 60% to 100%, and the deuterium content of Structural Formulas A and B may be 0%.

In another exemplary embodiment, the deuterium content of Structural Formula C may be 70% to 100%, and the deuterium content of Structural Formulas A and B may be 0%.

In another exemplary embodiment, the deuterium content of Structural Formula C may be 80% to 100%, and the deuterium content of Structural Formulas A and B may be 0%.

In another exemplary embodiment, the deuterium content of Structural Formula C may be 100%, and the deuterium content of Structural Formulas A and B may be 0%.

When intramolecular electron transport occurs, electrons move in the unshared electron pair of the P orbital in the nitrogen part of Formula 1, and radicals can be generated. Therefore, when Structural Formula C is substituted with deuterium, the stability of radicals generated in the biscarbazole moiety can be increased, and thus holes can be more stably received and transferred. Since the probability of radical generation due to intramolecular electron transport in the P orbital of biscarbazole is higher than in structural formula A and structural formula B, drive and life characteristics than compounds in which structural formula A and structural formula B are substituted with deuterium this is excellent

In an OLED device, the recombination zone has excellent efficiency and lifetime as it is located in the center of the light emitting layer. In Formula 2 of the present invention, since the electron transfer rate is relatively higher than the hole transfer rate, the recombination zone is biased to one side. When the deuterium-substituted compound of Chemical Formula 1 is used in a device in combination, molecules are more densely packed in the device. Therefore, the intermolecular distance is closer, allowing electrons and holes to move faster. In particular, when a compound in which structural formula C, which is a hole receiving part, is substituted with deuterium is used in combination with formula 2, the efficiency and lifespan can be improved by improving the movement speed of holes and locating the recombination zone in the center. there is.

In one embodiment of the present application, the content of deuterium in Structural Formulas A to C may be 50% to 100%.

In another exemplary embodiment, the deuterium content of Structural Formulas A to C may be 60% to 100%.

In another exemplary embodiment, the deuterium content of Structural Formulas A to C may be 70% to 100%.

In another exemplary embodiment, the deuterium content of Structural Formulas A to C may be 100%.

As described above, when the compound of Formula 1 of the present invention is substituted with 100% deuterium, when the structural formulas A and B are substituted with deuterium; And the effect of the case where the structural formula C is substituted with deuterium may have an effect of improving the lifespan, efficiency and driving of the light emitting device.

In an exemplary embodiment of the present application, R, R', and R" are the same as or different from each other and each independently represents a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group. it can be

In another exemplary embodiment, R, R', and R" are the same as or different from each other and each independently may be a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group.

In another exemplary embodiment, R, R', and R" are the same as or different from each other and each independently may be a substituted or unsubstituted C1 to C60 alkyl group; or a substituted or unsubstituted C6 to C60 aryl group there is.

In another exemplary embodiment, R, R', and R" are the same as or different from each other, and each independently may be a C1 to C60 alkyl group; or a C6 to C60 aryl group.

In another exemplary embodiment, R, R', and R" are the same as or different from each other and may each independently be a substituted or unsubstituted methyl group; or a substituted or unsubstituted phenyl group.

In another exemplary embodiment, R, R', and R" are the same as or different from each other, and each independently may be a methyl group; or a phenyl group.

In another exemplary embodiment, R, R', and R" may be a phenyl group.

In one embodiment of the present application, L3 is a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group.

In another exemplary embodiment, L3 is a direct bond; A substituted or unsubstituted C6 to C40 arylene group; Or a substituted or unsubstituted C2 to C40 heteroarylene group.

In another exemplary embodiment, L3 is a direct bond; Or a substituted or unsubstituted C6 to C40 arylene group.

In another exemplary embodiment, L3 is a direct bond; or a C6 to C40 arylene group.

In another exemplary embodiment, L3 is a direct bond; or a C6 to C20 arylene group.

In another exemplary embodiment, L3 is a direct bond; or a C6 to C10 monocyclic arylene group.

In another exemplary embodiment, L3 is a direct bond; Or a substituted or unsubstituted phenylene group.

In another exemplary embodiment, L3 is a direct bond; or a phenylene group.

In an exemplary embodiment of the present application, Ra, Rb, and Rc are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group;

In another exemplary embodiment, Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group;

In another exemplary embodiment, Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1 to C40 alkyl group; A substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group;

In another exemplary embodiment, Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; heavy hydrogen; C1 to C40 alkyl group; C6 to C40 aryl group; or a C2 to C40 heteroaryl group;

In another exemplary embodiment, Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; heavy hydrogen; C6 to C20 aryl group; or a C2 to C20 heteroaryl group;

In another exemplary embodiment, Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuran group; or a substituted or unsubstituted dibenzothiophene group;

In another exemplary embodiment, Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; heavy hydrogen; phenyl group; biphenyl group; Dibenzofuran group; or a dibenzothiophene group;

In one embodiment of the present application, A is a substituted or unsubstituted C6 to C20 arylene group; Or it may be a substituted or unsubstituted C2 to C20 heteroarylene group.

In another exemplary embodiment, A is a substituted or unsubstituted C6 to C10 arylene group; Or it may be a substituted or unsubstituted C2 to C10 heteroarylene group.

In another exemplary embodiment, A is a C6 to C10 arylene group; Or it may be a C2 to C10 heteroarylene group.

In another exemplary embodiment, A is a C6 to C10 monocyclic arylene group; Or it may be a heteroarylene group containing O or S of C2 to C10.

In another exemplary embodiment, A is a substituted or unsubstituted divalent phenylene group; A substituted or unsubstituted divalent dibenzofuran group; or a substituted or unsubstituted divalent dibenzothiophene group.

In another exemplary embodiment, A is a divalent phenylene group; Divalent dibenzofuran group; or a divalent dibenzothiophene group.

In one embodiment of the present application, Ar3 is a substituted or unsubstituted carbazole group; A substituted or unsubstituted C10 to C60 aryl group; Alternatively, it may be a C2 to C60 heteroaryl group containing O or S as a substituted or unsubstituted heterogeneous element.

In another exemplary embodiment, Ar3 is a substituted or unsubstituted carbazole group; A substituted or unsubstituted C10 to C40 aryl group; Alternatively, it may be a C2 to C40 heteroaryl group containing O or S as a substituted or unsubstituted heterogeneous element.

In another exemplary embodiment, Ar3 is a substituted or unsubstituted carbazole group; A substituted or unsubstituted C10 to C20 aryl group; Alternatively, it may be a C2 to C20 heteroaryl group containing O or S as a substituted or unsubstituted heterogeneous element.

In another exemplary embodiment, Ar3 is a carbazole group unsubstituted or substituted with a C6 to C10 aryl group; C10 to C20 aryl group; Or it may be a C2 to C20 heteroaryl group containing O or S as a heterogeneous element.

In another exemplary embodiment, Ar3 is a carbazole group unsubstituted or substituted with a C6 to C10 aryl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophene group.

In another exemplary embodiment, Ar3 is a carbazole group unsubstituted or substituted with a C6 to C10 aryl group; biphenyl group; triphenylenyl group; Dibenzofuran group; or a dibenzothiophene group.

In another exemplary embodiment, Ar3 may be represented by any one of Chemical Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

Ar13 is a substituted or unsubstituted C10 to C60 aryl group,

R21 to R28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

Y is O; or S,

a is an integer from 0 to 3, and when a is 2 or more, the substituents in parentheses are the same as or different from each other.

In one embodiment of the present application, Ar13 may be a substituted or unsubstituted C10 to C60 aryl group.

In another exemplary embodiment, Ar13 may be a substituted or unsubstituted C10 to C40 aryl group.

In another exemplary embodiment, Ar13 may be a substituted or unsubstituted C10 to C20 aryl group.

In another exemplary embodiment, Ar13 is a biphenyl group; Or a triphenylenyl group; it may be.

In an exemplary embodiment of the present application, R21 to R28 are the same as or different from each other and each independently hydrogen; heavy hydrogen; halogen group; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, R21 to R28 are the same as or different from each other and each independently hydrogen; heavy hydrogen; Or it may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R21 to R28 are the same as or different from each other and each independently hydrogen; heavy hydrogen; Or it may be a C6 to C60 aryl group.

In another exemplary embodiment, R21 to R28 are the same as or different from each other and each independently hydrogen; heavy hydrogen; Or it may be a C6 to C40 aryl group.

In another exemplary embodiment, R21 to R28 are the same as or different from each other and each independently hydrogen; heavy hydrogen; Or it may be a C6 to C20 aryl group.

In another exemplary embodiment, R21 to R28 are the same as or different from each other and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted phenyl group; may be.

In another exemplary embodiment, R21 to R28 are the same as or different from each other and each independently hydrogen; heavy hydrogen; Or a phenyl group; it may be.

In an exemplary embodiment of the present application, A may be represented by any one of Formulas 3 to 5 below.

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,

Y1 is O; or S,

는 상기 화학식 2의

와 연결되는 위치를 의미하고,

Is the formula (2)

means the position connected to,

는 상기 화학식 2의

와 연결되는 위치를 의미한다.

Is the formula (2)

means a location connected to

the compound of Formula 1; And when the compound of Formula 2 is included in the organic material layer of the organic light emitting device, more excellent efficiency and lifespan effects are shown. This result can be expected that an exciplex phenomenon occurs when the two compounds are included at the same time.

The exciplex phenomenon is a phenomenon in which energy of the size of the HOMO level of the donor (p-host) and the LUMO level of the acceptor (n-host) is released through electron exchange between two molecules. When the exciplex between two molecules occurs, Reverse Intersystem Crossing (RISC) occurs, and this can increase the internal quantum efficiency of fluorescence to 100%. When a donor (p-host) with good hole transport ability and an acceptor (n-host) with good electron transport capability are used as the host of the light emitting layer, holes are injected into the p-host and electrons are injected into the n-host. can be lowered, thereby helping to improve the lifespan.

In an exemplary embodiment of the present application, Formula 1 may be represented by any one of the following compounds.

In an exemplary embodiment of the present application, the heterocyclic compound represented by Chemical Formula 2 may be any one selected from the following compounds.

In addition, by introducing various substituents into the structures of Chemical Formulas 1 and 2, compounds having unique characteristics of the introduced substituents can be synthesized. For example, by introducing substituents mainly used in hole injection layer materials, hole transport materials, light emitting layer materials, electron transport layer materials, and charge generation layer materials used in the manufacture of organic light emitting devices into the core structure, the requirements of each organic layer are met. substances can be synthesized.

In addition, by introducing various substituents into the structures of Formulas 1 and 2, it is possible to finely control the energy band gap, while improving the properties at the interface between organic materials and diversifying the use of materials. .

Meanwhile, the heterocyclic compound has a high glass transition temperature (Tg) and excellent thermal stability. This increase in thermal stability is an important factor in providing driving stability to the device.

The heterocyclic compound according to an exemplary embodiment of the present application may be prepared through a multi-step chemical reaction. Some intermediate compounds are prepared first, and the compounds of Formula 1 or 2 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application may be prepared based on Preparation Examples described below.

In addition, another exemplary embodiment of the present application provides a composition for an organic layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 above.

Details of the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are the same as described above.

The weight ratio of the heterocyclic compound represented by Formula 1 in the composition to the heterocyclic compound represented by Formula 2 may be 1: 10 to 10: 1, 1: 8 to 8: 1, or 1: 5 to 5:1, or 1:2 to 2:1, but is not limited thereto.

The composition can be used when forming an organic material of an organic light emitting device, and can be more preferably used when forming a host of a light emitting layer.

The composition is in the form of simple mixing of two or more compounds, and powder materials may be mixed before forming the organic material layer of the organic light emitting device, or liquid compounds may be mixed at an appropriate temperature or higher. The composition is in a solid state below the melting point of each material, and can be maintained in a liquid state by adjusting the temperature.

The composition may further include materials known in the art, such as solvents and additives.

The organic light emitting device according to an exemplary embodiment of the present application uses a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2, except that one or more organic material layers are formed. It can be manufactured by the manufacturing method and material of the light emitting element.

The compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as organic material layers. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.

Specifically, the organic light emitting device according to an exemplary embodiment of the present application includes a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode, and at least one layer of the organic material layers is It includes the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 above.

In one embodiment of the present application, the first electrode may be an anode, and the second electrode may be a cathode.

In another exemplary embodiment, the first electrode may be a cathode and the second electrode may be an anode.

In an exemplary embodiment of the present application, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound according to Formula 1 and the heterocyclic compound according to Formula 2 may be used as materials for the blue organic light emitting device. .

In an exemplary embodiment of the present application, the organic light emitting device may be a green organic light emitting device, and the compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be used as materials for the green organic light emitting device. .

In an exemplary embodiment of the present application, the organic light emitting device may be a red organic light emitting device, and the compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be used as materials for the red organic light emitting device. .

The organic light emitting device of the present invention includes a light emitting layer, a hole injection layer, and a hole transport layer. One layer or two or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer may be further included.

In an exemplary embodiment of the present application, the organic material layer includes at least one layer of a hole blocking layer, an electron injection layer, and an electron transport layer, and at least one layer of the hole blocking layer, the electron injection layer, and the electron transport layer is represented by Chemical Formula 1. It provides an organic light emitting device comprising the heterocyclic compound represented by the above formula and the heterocyclic compound represented by Formula 2.

In an exemplary embodiment of the present application, the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2. Provide an organic light emitting device. do.

In an exemplary embodiment of the present application, the organic material layer includes a light emitting layer, the light emitting layer includes a host material, and the host material is a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2 It provides an organic light emitting device comprising a.

1 to 3 illustrate the stacking order of the electrode and the organic material layer of the organic light emitting device according to an exemplary embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and structures of organic light emitting devices known in the art may be applied to the present application as well.

According to FIG. 1 , an organic light emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown. However, it is not limited to such a structure, and as shown in FIG. 2, an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented.

3 illustrates a case where the organic material layer is multi-layered. The organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, an emission layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a laminated structure, and layers other than the light emitting layer may be omitted as necessary, and other necessary functional layers may be further added.

In one embodiment of the present application, preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the organic material layer includes forming one or more organic material layers using the composition for an organic material layer according to an exemplary embodiment of the present application. A method for manufacturing an organic light emitting device is provided.

In an exemplary embodiment of the present application, the forming of the organic material layer is formed by pre-mixing the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 using a thermal vacuum deposition method. A method for manufacturing a phosphorus organic light emitting device is provided.

The pre-mixing means mixing the materials first before depositing the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 on the organic material layer and mixing them in one park.

The premixed material may be referred to as a composition for an organic layer according to an exemplary embodiment of the present application.

In the organic light emitting device according to an exemplary embodiment of the present application, materials other than the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 are exemplified below, but these are for illustrative purposes only and do not limit the scope of the present application. It is not intended to be limiting, and materials known in the art may be substituted.

Materials having a relatively high work function may be used as the anode material, and transparent conductive oxides, metals, or conductive polymers may be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

Materials having a relatively low work function may be used as the cathode material, and metals, metal oxides, or conductive polymers may be used. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

As the hole injection material, a known hole injection material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in [Advanced Material, 6, p.677 (1994)] starburst amine derivatives, such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine (m- MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid, a soluble conductive polymer, or poly( 3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate) (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), Polyaniline/Camphor sulfonic acid or Polyaniline/ Poly(4-styrene-sulfonate) or the like can be used.

As the hole transport material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used, and low molecular weight or high molecular weight materials may also be used.

Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone. Derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, etc. may be used, and high molecular materials as well as low molecular materials may be used.

As an electron injection material, for example, LiF is typically used in the art, but the present application is not limited thereto.

A red, green or blue light emitting material may be used as the light emitting material, and if necessary, two or more light emitting materials may be mixed and used. In this case, two or more light emitting materials may be deposited and used as individual sources, or may be pre-mixed and deposited as one source. In addition, a fluorescent material can be used as a light emitting material, but it can also be used as a phosphorescent material. As the light emitting material, a material that emits light by combining holes and electrons respectively injected from the anode and the cathode may be used, but materials in which a host material and a dopant material are involved in light emission may also be used.

When the host of the light emitting material is mixed and used, hosts of the same series may be mixed and used, or hosts of different series may be mixed and used. For example, two or more materials selected from among n-type host materials and p-type host materials may be selected and used as host materials for the light emitting layer.

An organic light emitting device according to an exemplary embodiment of the present application may be a top emission type, a bottom emission type, or a double side emission type depending on materials used.

The heterocyclic compound according to an exemplary embodiment of the present application may act on a principle similar to that applied to an organic light emitting device in an organic electronic device including an organic solar cell, an organic photoreceptor, and an organic transistor.

Hereinafter, the present specification will be described in more detail through examples, but these are only for exemplifying the present application, and are not intended to limit the scope of the present application.

< manufacturing example >

[ manufacturing example 1] Preparation of Compound 1-2 (B)

1) Preparation of Intermediate 1-2-1

In a one-necked round bottom flask, 9H,9'H-3,3'-bicarbazole (10 g, 0.030 mol), 4-bromo-1,1'-Biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ (4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ ) [A] (7.26g, 0.030mol), CuI (0.57g, 0.003mol), trans-1,2-diaminocyclohexane (Trans- 1,2-diaminocyclohexane) (0.34g, 0.003mol) and K ₃ PO ₄ (12.74g, 0.06mol) were dissolved in 100mL of 1,4-dioxane and refluxed at 125℃ for 8 hours. did After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) and recrystallized from methanol to obtain intermediate 1-2-1. (13.92 g, yield 94%)

2) Preparation of compound 1-2

In a one-neck round bottom flask, intermediate 1-2-1 (13.92 g, 0.028 mol), 4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ (4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ ) [A'] (6.83g, 0.028mol), CuI (0.53g, 0.0028mol), trans-1,2-diaminocyclohexane (0.32g, 0.0028mol), K ₃ PO ₄ (11.89g, 0.056mol) in 1,4 - After dissolving in 140mL of dioxane, it was refluxed at 125℃ for 8 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) and recrystallized from methanol to obtain the target compound 1-2. (16.14 g, yield 88%)

When Compound A and Compound A' are the same, the target compound can be directly synthesized by adding 2 equivalents of Compound A in Preparation Example 1 above. That is, when Compound A and Compound A' are the same, Preparation Example 1-2 may be omitted.

In Preparation Example 1, 4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ [A], 4 -Bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ Compounds A and A of Table 1 instead of [A'] ' was synthesized in the same manner as in Preparation Example 1 except for using ', and the following target compound B was synthesized in the same manner.

[ manufacturing example 2] Preparation of Compound 1-26 (D)

1) Preparation of Intermediate 1-26-1

In a one-necked round bottom flask, 9H,9'H-3,3'-bicarbazole (10 g, 0.030 mol), Triflic acid (112.56 g, 0.75 mol) and D ₆ -Benzene (500 mL) was _refluxed at 40 °C. After concentration by quenching and extraction with DMC and H ₂ O, a silica gel filter was applied. After concentration, treatment with methanol gave intermediate 1-26-1. (7.07 g, yield 68%)

2) Preparation of Intermediate 1-26-2

In a one-necked round bottom flask, intermediate 1-26-1 (7.07 g, 0.02 mol), CuI (0.38 g, 0.002 mol), 4-bromo-1,1'-biphenyl (4-bromo-1,1' -biphenyl) [C] (4.66 g, 0.02 mol), trans-1,2-diaminocyclohexane (0.23 g, 0.002 mol), K ₃ PO ₄ (8.49 g, 0.04 mol) in 1,4-dioxane After dissolving in 70mL, it was refluxed at 125℃ for 8 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reactant was purified by column chromatography (DCM:Hexane=1:3) and recrystallized from methanol to obtain intermediate 1-26-2. (8.28 g, yield 83%)

3) Preparation of compound 1-26

In a one-neck round bottom flask, intermediate 1-26-2 (8.28 g, 0.017 mol), CuI (0.32 g, 0.0017 mol), 4-bromo-1,1'-biphenyl (4-bromo-1,1' -biphenyl) [C'] (3.96 g, 0.017 mol), trans-1,2-diaminocyclohexane (0.19 g, 0.0017 mol), K ₃ PO ₄ (7.22 g, 0.034 mol) were mixed with 1,4-di After dissolving in oxane 80mL, it was refluxed at 125℃ for 8 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) and recrystallized from methanol to obtain the target compound 1-26. (8.63 g, yield 78%)

When compound C and compound C' are the same, the target compound can be directly synthesized by adding 2 equivalents of compound C in Preparation Example 2-2. That is, when Compound C and Compound C' are the same, Preparation Example 2-3 may be omitted.

In Preparation Example 2, 4-bromo-1,1'-biphenyl [C], 4-bromo-1,1'-biphenyl [C'] instead of compounds C and C' of Table 2 It was synthesized in the same manner as in Preparation Example 2 except for the use, and the following target compound D was synthesized in the same manner.

As a result of the reaction condition test experiment under the same conditions as in Examples 1 to 4 in Table 3 below, it was confirmed that compound 1-26-1 was not synthesized.

In the reaction of substituting deuterium for hydrogen in an organic compound, the higher the reaction temperature, the higher the substitution rate of hydrogen to deuterium, and the lower the yield. Here, the substitution rate is calculated as [(the number of deuterium substituted after the chemical reaction) / (the number of hydrogens in the compound before the chemical reaction)] * 100.

As can be seen in Table 4, compound 1-26-1 was synthesized under the reaction conditions of Example 7 with the highest substitution rate.

[ manufacturing example 3] Preparation of compound 1-50 (G)

1) Preparation of Intermediate 1-50-1

9-([1,1'-biphenyl]-4-yl)-9H,9'H-3,3'-bicarbazole (9-([ 1,1'-biphenyl]-4-yl)-9H,9'H-3,3'-bicarbazole) [E] (10 g, 0.021 mol), 4-bromo-1,1'-biphenyl (4 -bromo-1,1'-biphenyl) [F] (4.90 g, 0.021 mol), CuI (0.40 g, 0.0021 mol), trans-1,2-diaminocyclohexane (0.024 g, 0.0021 mol), K ₃ After dissolving PO ₄ (8.92g, 0.042mol) in 100mL of 1,4-dioxane, the mixture was refluxed at 125°C for 8 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) and recrystallized from methanol to obtain intermediate 1-50-1. (12.17 g, yield 91%)

2) Preparation of compound 1-50

A mixture of intermediate 1-50-1 (12.17 g, 0.017 mol), triflic acid (63.78 g, 0.43 mol) and D ₆ -benzene (600 mL) was placed in a _one -necked round bottom flask. It was refluxed at 50°C. After quenching and extraction with DCM and H ₂ O and concentration, a silica gel filter was performed. After concentration, methanol treatment was performed to obtain the target compound 1-50. (8.87 g, yield 78%)

In Preparation Example 3, 9-([1,1'-biphenyl]-4-yl)-9H,9'H-3,3'-bicarbazole [E] , 4-bromo-1, The target compound G was synthesized in the same manner as in Preparation Example 3, except that compounds E and F of Table 5 were used instead of 1'-biphenyl [F] .

As a result of the reaction condition test experiment under the same conditions as in Examples 1 to 4 in Table 6 below, it was confirmed that compound 1-50 was not synthesized.

In the reaction of substituting deuterium for hydrogen in an organic compound, the higher the reaction temperature, the higher the substitution rate of hydrogen to deuterium, and the lower the yield. Here, the substitution rate is calculated as [(the number of deuterium substituted after the chemical reaction) / (the number of hydrogens in the compound before the chemical reaction)] * 100.

As can be seen in Table 7, compound 1-50 was synthesized under the reaction conditions of Example 7 having the highest substitution rate.

[ manufacturing example 4] Preparation of Compound 2-9 (K)

1) Preparation of Intermediate 2-9-1

7-chloro-2-fluorodibenzo[b,d]furan (6 g, 27.19 mmol), 9H- A mixture of carbazole (5g, 29.9mmol), Cs ₂ CO ₃ (22g, 101.7mmol), and dimethylacetamide (60ml) was refluxed at 170°C for 12h. After cooling, the filtrate was filtered, and the solvent was removed from the filtrate, followed by column purification at HX:MC = 3:1 to obtain compound 2-9-1 (9g, 90%).

2) Preparation of Intermediate 2-9-2

9-(7-chlorodibenzo[b,d]furan-2-yl)-9H-carbazole (9-(7-chlorodibenzo[b,d]furan-2 -yl)-9H-carbazole) (9g, 24.4 mmol), bis(pinacolato)diboron (12.4g, 48.9mmol), Pcy ₃ (1.37g, 4.89mmol), potassium acetate (7.1g, 73mmol), A mixture of Pd ₂ (dba) ₃ (2.2 g, 2.44 mmol) in 1,4-dioxane (100 ml) was refluxed at 140 °C. After cooling, the filtered filtrate was concentrated and column purified HX:MC = 3:1 to obtain compound 2-9-2 (7.2g, 64%).

3) Preparation of compounds 2-9

9-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d ]furan-2-yl)-9H-carbazole (9-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-2 -yl)-9H-carbazole) (7.2g, 15.6mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine) (5.90g, 17.16mmol), tetrakis(triphenylphosphine) A mixture of palladium(0) (0.90 g, 0.78 mmol), potassium carbonate (4.31 g, 31.2 mmol), and 1,4-dioxane/water (100 ml/25 ml) was refluxed at 120° C. for 4 hours. After filtering at 120 °C, the mixture was washed with 120 °C 1,4-dioxane, distilled water, and MeOH to obtain compound 2-9[K]. (7.50g, 75%)

In Preparation Example 4, it was synthesized in the same manner as in Preparation Example 4, except that Compounds H, I and J of Table 8 were used.

[ manufacturing example 5] Preparation of Compound 2-13 (K)

1) Preparation of Intermediate 2-13-1

7-chloro-2-fluorodibenzo[b,d]furan (6 g, 27.19 mmol), [1 ,1'-biphenyl]-4-ylboronic acid ([1,1'-biphenyl]-4-ylboronic acid) (5.92g, 29.91mmol), tetrakis(triphenylphosphine)palladium(0)(1.69g , 1.46 mmol), potassium carbonate (7.52 g, 54.38 mmol), and 1,4-dioxane/water (60 ml/15 ml) mixture was refluxed at 120 ^° C. for 4 hours. After filtering at 120°C, the mixture was washed with 1,4-dioxane, distilled water and MeOH at 120°C to obtain compound 2-13-1. (7.53g, 78%)

2) Preparation of Intermediate 2-13-2

2-([1,1'-biphenyl]-4-yl)-7-chlorodibenzo[b,d]furan (2-([1,1'- biphenyl]-4-yl)-7-chlorodibenzo[b,d]furan) (7.53g, 21.22mmol), bis(pinacolato)diboron (10.78g, 42.44mmol), Pcy ₃ (1.19g, 4.24mmol) ), potassium acetate (6.25g, 63.66mmol), Pd ₂ (dba) ₃ (1.94g, 2.12mmol) in 1,4-dioxane (70ml) mixture was refluxed at 140 ℃. After cooling, the filtered filtrate was concentrated to obtain compound 2-13-2 (6.25g, 66%) by column purification HX:MC = 3:1.

3) Preparation of compound 2-13

2-(8-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-3-yl)-4,4,5 ,5-Tetramethyl-1,3,2-dioxaborolane (2-(8-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-3-yl)- 4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (6.25 g, 14.00 mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6- Phenyl-1,3,5-triazine (2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine) (5.29g, 15.4mmol ), tetrakis (triphenylphosphine) palladium (0) (0.81 g, 0.7 mmol), potassium carbonate (3.87 g, 28.00 mmol), 1,4-dioxane / water (60 ml / 18 ml) mixture at 120 ℃ Refluxed for 4 hours. After filtering at 120 ° C., the mixture was washed with 120 ^° C 1,4-dioxane, distilled water and MeOH to obtain compound 2-13 [O]. (6.77g, 77%)

In Preparation Example 5, it was synthesized in the same manner as in Preparation Example 5, except that the compounds L, M and N of Table 9 were used.

Compounds of Formula 1 and Formula 2 other than the compounds described in Preparation Examples 1 to 5 were also prepared in the same manner as described in Preparation Examples.

Table 10 and Table 11 below are FD-MS data and ¹ H NMR data of the synthesized compounds, and it can be confirmed that the target compound was synthesized through the following data.

compound FD-Mass compound FD-Mass 1-2 m/z= 654.91 (C48H14D18N2=654.37) 1-3 m/z= 574.79 (C42H14D14N2=574.31) 1-5 m/z= 654.91 (C48H14D18N2=654.37) 1-6 m/z= 654.91 (C48H14D18N2=654.37) 1-8 m/z= 654.91 (C48H14D18N2=654.37) 1-19 m/z= 815.15 (C60H14D26N2=814.48) 1-22 m/z= 815.15 (C606H14D26N2=814.48) 1-26 m/z= 650.88 (C48H18D14N2=650.34) 1-27 m/z= 574.79 (C42H14D14N2=574.31) 1-29 m/z= 650.88 (C48H18D14N2=650.34) 1-32 m/z= 650.88 (C48H18D14N2=650.34) 1-33 m/z= 650.88 (C48H18D14N2=650.34) 1-36 m/z = 726.98 (C54H22D14N2=726.38) 1-39 m/z = 726.98 (C54H22D14N2=726.38) 1-44 m/z = 664.87 (C48H16D14N2O=664.32) 1-50 m/z= 668.99 (C48D32N2=668.46) 1-51 m/z= 588.87 (C42D28N2=588.40) 1-53 m/z= 668.99 (C48D32N2=668.46) 1-54 m/z= 668.99 (C48D32N2=668.46) 1-56 m/z= 668.99 (C48D32N2=668.46) 1-57 m/z= 668.99 (C48D32N2=668.46) 1-58 m/z= 749.12 (C54D36N2=748.51) 1-60 m/z= 749.12 (C54D36N2=748.51) 1-62 m/z= 749.12 (C54D36N2=748.51) 1-63 m/z= 749.12 (C54D36N2=748.51) 1-67 m/z= 829.24 (C60D40N2=828.57) 1-68 m/z= 680.96 (C48D30N2O=680.42) 2-9 m/z= 640.75 (C45H28N4O=640.23) 2-10 m/z= 716.84 (C51H32N4O=716.26) 2-11 m/z= 640.75 (C45H28N4O=640.23) 2-13 m/z= 627.75 (C45H29N3O=627.23) 2-14 m/z= 627.75 (C45H29N3O=627.23) 2-16 m/z = 703.85 (C51H33N3O=703.26) 2-21 m/z= 581.69 (C39H23N3OS=581.16) 2-32 m/z= 656.81 (C45H28N4S=656.20) 2-55 m/z= 654.73 (C45H26N4O2=654.21) 2-56 m/z= 654.73 (C45H26N4O2=654.21)

compound ¹ H NMR (DMSO, 300 Mz) 1-2 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.19 (2H, m), 7.89 to 7.99 (4H, m), 7.77 (1H, d), 7.50 to 7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, m) 1-3 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.19 (2H, m), 7.89 to 7.99 (4H, m), 7.77 (1H, d), 7.50 to 7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, m) 1-5 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.19 (2H, m), 7.89 to 7.99 (4H, m), 7.77 (1H, d), 7.50 to 7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, m) 1-6 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.19 (2H, m), 7.89 to 7.99 (4H, m), 7.77 (1H, d), 7.50 to 7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, m) 1-8 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.19 (2H, m), 7.89 to 7.99 (4H, m), 7.77 (1H, d), 7.50 to 7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, m) 1-19 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.19 (2H, m), 7.89 to 7.99 (4H, m), 7.77 (1H, d), 7.50 to 7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, m) 1-22 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.19 (2H, m), 7.89 to 7.99 (4H, m), 7.77 (1H, d), 7.50 to 7.58 (2H, m), 7.35 (1H, t), 7.16~7.20 (2H, m) 1-26 δ = 7.91~7.92 (8H, m), 7.75 (4H, d), 7.41~7.49 (6H, m) 1-27 δ = 8.21 (1H, s), 7.41~7.75 (13H, m) 1-29 δ = 7.91~7.94 (5H, m), 7.73~7.75 (3H, m), 7.41~7.62 (10H, m) 1-32 δ = 8.21 (1H, s), 7.60~7.75 (8H, m), 7.41~7.49 (8H, m) 1-33 δ = 8.21 (1H, s), 7.91 to 7.92 (4H, m), 7.60 to 7.75 (6H, m), 7.41 to 7.49 (7H, m) 1-36 δ = 8.21 (1H, s), 7.91 to 7.92 (4H, m), 7.60 to 7.75 (6H, m), 7.41 to 7.49 (7H, m), 7.25 (4H, s) 1-39 δ = 7.91~7.92 (8H, m), 7.75 (4H, d), 7.41~7.49 (6H, m), 7.25 (4H, s) 1-50 δ = no ¹ H NMR peak with 100% deuterium content 1-51 δ = no ¹ H NMR peak with 100% deuterium content 1-53 δ = no ¹ H NMR peak with 100% deuterium content 1-54 δ = no ¹ H NMR peak with 100% deuterium content 1-56 δ = no ¹ H NMR peak with 100% deuterium content 1-57 δ = no ¹ H NMR peak with 100% deuterium content 1-58 δ = no ¹ H NMR peak with 100% deuterium content 1-60 δ = no ¹ H NMR peak with 100% deuterium content 1-62 δ = no ¹ H NMR peak with 100% deuterium content 1-63 δ = no ¹ H NMR peak with 100% deuterium content 1-67 δ = no ¹ H NMR peak with 100% deuterium content 2-9 δ = 8.55 (1H, d), 8.36 (2H, m), 8.19 (1H, d), 7.94 to 8.03 (4H, m), 7.74 to 7.82 (5H, m), 7.16 to 7.61 (15H, m) 2-10 δ = 8.55 (1H, d), 8.36 (2H, m), 7.89 to 8.03 (6H, m), 7.74 to 7.76 (8H, m), 7.61 (1H, s), 7.25 to 7.50 (13H, m), 7.16 (1H, t) 2-11 δ = 8.55 (1H, d), 8.36~8.38 (3H, m), 8.19 (1H, d), 7.94~8.03 (4H, m), 7.73~7.82 (5H, m), 7.35~7.61 (11H, m) ), 7.16~7.25 (3H, m) 2-13 δ = 8.36 (2H, m), 7.96 to 8.03 (3H, m), 7.75 to 7.88 (9H, m), 7.41 to 7.50 (9H, m), 7.25 (6H, m) 2-14 δ = 8.36 (2H, m), 7.73–8.03 (14H, m), 7.61 (2H, d), 7.41–7.50 (9H, m), 7.25 (2H, d) 2-16 δ = 8.36 (2H, m), 7.94–8.03 (4H, m), 7.73–7.82 (9H, m), 7.41–7.61 (12H, m), 7.25 (6H, m) 2-21 δ = 8.45 (1H, d), 8.36 (4H, m), 8.17 to 8.24 (3H, m), 8.03 (1H, d), 7.76 to 7.93 (6H, m), 7.49 to 7.56 (8H, m) 2-32 δ = 8.55 (1H, d), 8.36 (2H, m), 8.19 to 8.24 (3H, m), 7.89 to 7.96 (5H, m), 7.75 (2H, d), 7.35 to 7.63 (11H, m), 7.16~7.25 (4H, m) 2-55 δ = 8.55 (1H, d), 8.36 (2H, m), 8.19 (1H, d), 7.74 to 8.08 (8H, m), 7.50 to 7.61 (8H, m), 7.31 to 7.39 (4H, m), 7.16~7.20 (2H, m) 2-56 δ = 8.55 (1H, d), 8.36 (2H, m), 8.19 (1H, d), 7.76 to 8.08 (8H, m), 7.50 to 7.58 (8H, m), 7.16 to 7.39 (6H, m)

< Experimental example 1>-Manufacture of organic light emitting device

A glass substrate coated with ITO thin film to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropyl alcohol, and after drying, UVO treatment was performed for 5 minutes using UV in a UV cleaner. Thereafter, the substrate was transferred to a plasma cleaner (PT), plasma treated to remove the ITO work function and residual film in a vacuum state, and transferred to a thermal evaporation equipment for organic deposition.

A hole injection layer 2-TNATA (4,4', 4"-Tris [2-naphthyl (phenyl) amino] triphenylamine) and a hole transport layer NPB (N, N'-diphenyl- (1,1'-biphenyl)-4,4'-diamine) was formed.

A light emitting layer was thermally vacuum deposited thereon as follows. The emission layer was deposited at 400 Å by doping the host with Ir(ppy) _{3 at 7% using a compound listed in Table 12 as a host and Ir(ppy) 3 (} tris(2-phenylpyridine)iridium) as a green phosphorescent dopant. Thereafter, 60 Å of BCP was deposited as a hole blocking layer, and 200 Å of Alq ₃ was deposited thereon as an electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited on the electron injection layer to a thickness of 1200 Å to form a cathode, thereby forming an organic electric field A light emitting device was manufactured.

On the other hand, all organic compounds required for OLED device fabrication were purified by vacuum sublimation under 10 ⁻⁶ to 10 ⁻⁸ torr for each material and used for OLED fabrication.

2) Organic electric field Driving voltage and luminous efficiency of light emitting device

The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured with McSyers' M7000, and the standard luminance was measured at 6,000 At cd/m ² , T ₉₀ was measured.

compound drive voltage
(V) efficiency
(cd/A) color coordinates
(x, y) life span
(T ₉₀ ) Comparative Example 1 A 6.11 44.1 Green 59 Comparative Example 2 B 6.15 45.5 62 Comparative Example 3 C 6.23 43.6 68 Comparative Example 4 D 6.48 42.9 60 Comparative Example 5 E 6.90 40.7 50 Comparative Example 6 1-2 5.68 55.4 90 Comparative Example 7 1-4 5.34 54.8 84 Comparative Example 8 1-5 5.48 53.9 88 Comparative Example 9 1-7 5.59 56.0 80 Comparative Example 10 1-8 5.61 55.8 86 Comparative Example 11 1-9 5.79 53.7 88 Comparative Example 12 1-26 3.71 74.6 130 Comparative Example 13 1-28 3.60 75.0 124 Comparative Example 14 1-29 3.88 68.7 128 Comparative Example 15 1-31 3.92 69.1 120 Comparative Example 16 1-32 3.67 70.5 126 Comparative Example 17 1-33 3.83 71.3 128 Comparative Example 18 1-50 4.03 70.3 150 Comparative Example 19 1-51 4.28 74.7 146 Comparative Example 20 1-52 4.16 75.1 142 Comparative Example 21 1-53 4.26 79.6 148 Comparative Example 22 1-55 4.33 77.5 138 Comparative Example 23 1-56 4.22 78.6 144 Comparative Example 24 1-57 4.50 73.2 148

In Table 12, when the compound 1 of the present application was included alone in the device, it was confirmed that driving was not good and efficiency and lifespan were lowered compared to the organic light emitting device of the combination of Formula 1 and Formula 2 described below.

< Experimental example 2>-Manufacture of organic light emitting device

A glass substrate coated with ITO thin film to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropyl alcohol, and after drying, UVO treatment was performed for 5 minutes using UV in a UV cleaner. Thereafter, the substrate was transferred to a plasma cleaner (PT), plasma treated to remove the ITO work function and residual film in a vacuum state, and transferred to a thermal evaporation equipment for organic deposition.

A hole injection layer 2-TNATA (4,4′,4′′-Tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB (N,N′-Di) as a common layer on the ITO transparent electrode (anode) (1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

A light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was pre-mixed with one compound shown in Formula 1 and one compound shown in Formula 2 in Table 13 as a host, deposited at 400 Å in one park after preliminary mixing, and the green phosphorescent dopant was Ir(ppy) ₃ deposited on the light emitting layer. It was deposited by doping 7% of the thickness. Thereafter, 60 Å of BCP was deposited as a hole blocking layer, and 200 Å of Alq ₃ was deposited thereon as an electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode. An electroluminescent device was manufactured.

On the other hand, all organic compounds required for OLED device fabrication were purified by vacuum sublimation under 10 ⁻⁶ to 10 ⁻⁸ torr for each material and used for OLED fabrication.

The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured with McSyers' M7000, and the standard luminance was measured at 6,000 At cd/m ² , T ₉₀ was measured.

The results of measuring the driving voltage, luminous efficiency, color coordinates (CIE), and lifetime of the organic light emitting device manufactured according to the present invention are shown in Table 13 below.

light emitting layer
compound ratio driving voltage
(V) efficiency
(cd/A) color coordinates
(x, y) life span
(T ₉₀ ) Comparative Example 6 [A]: 2-10 1:1 5.26 57.3 Green 82 Comparative Example 7 2:1 5.22 56.2 86 Comparative Example 8 3:1 5.13 55.6 89 Comparative Example 9 [B]: 2-21 1:1 5.36 56.3 Green 83 Comparative Example 10 2:1 5.21 55.7 87 Comparative Example 11 3:1 5.20 54.9 91 Comparative Example 12 [C]: 2-32 1:1 5.26 65.5 Green 89 Comparative Example 13 2:1 5.23 64.9 92 Comparative Example 14 3:1 5.18 64.3 95 Comparative Example 15 [D]: 2-16 1:1 5.19 57.9 Green 80 Comparative Example 16 2:1 5.11 57.1 83 Comparative Example 17 3:1 5.09 56.7 88 Comparative Example 18 [E]: 2-13 1:1 5.25 64.0 Green 79 Comparative Example 19 2:1 5.16 63.5 82 Comparative Example 20 3:1 5.10 62.7 89 Example 20 1-2:2-13 1:1 4.71 79.3 Green 91 Example 21 2:1 4.59 78.6 95 Example 22 3:1 4.55 77.3 99 Example 23 1-4:2-16 1:1 4.49 72.6 Green 92 Example 24 2:1 4.41 71.8 93 Example 25 3:1 4.38 70.6 98 Example 26 1-5:2-14 1:1 4.50 79.3 Green 90 Example 27 2:1 4.43 78.6 92 Example 28 3:1 4.41 77.1 95 Example 29 1-7:2-32 1:1 4.30 76.7 Green 93 Example 30 2:1 4.22 75.2 97 Example 31 3:1 4.19 74.6 100 Example 32 1-8:2-11 1:1 4.49 79.5 Green 96 Example 33 2:1 4.42 78.6 99 Example 34 3:1 4.38 77.3 102 Example 35 1-9:2-16 1:1 4.19 73.3 Green 95 Example 36 2:1 4.12 71.6 98 Example 37 3:1 4.03 70.3 105 Example 38 1-26:2-9 1:1 2.11 89.7 Green 150 Example 39 2:1 2.03 89.0 153 Example 40 3:1 1.98 88.1 158 Example 41 1-28:2-32 1:1 2.52 87.3 Green 161 Example 42 2:1 2.49 86.3 163 Example 43 3:1 2.46 85.7 165 Example 44 1-29:2-21 1:1 2.13 88.6 Green 155 Example 45 2:1 2.03 87.9 159 Example 46 3:1 1.94 87.1 163 Example 47 1-31:2-55 1:1 2.33 90.2 Green 162 Example 48 2:1 2.23 89.5 168 Example 49 3:1 2.15 88.3 170 Example 50 1-32:2-21 1:1 1.94 89.3 Green 154 Example 51 2:1 1.90 88.4 159 Example 52 3:1 1.83 87.7 168 Example 53 1-33:2-56 1:1 1.62 86.2 Green 155 Example 54 2:1 1.55 85.1 158 Example 55 3:1 1.53 84.3 165 Example 56 1-50: 2-10 1:1 4.02 110.3 Green 187 Example 57 2:1 3.98 108.3 190 Example 58 3:1 3.75 107.7 193 Example 59 1-51:2-16 1:1 3.87 100.5 Green 175 Example 60 2:1 3.76 99.4 179 Example 61 3:1 3.68 98.1 183 Example 62 1-52:2-55 1:1 3.65 107.8 Green 185 Example 63 2:1 3.60 106.2 188 Example 64 3:1 3.51 105.5 192 Example 65 1-53:2-14 1:1 3.72 108.9 Green 177 Example 66 2:1 3.61 107.2 180 Example 67 3:1 3.58 102.8 183 Example 68 1-55:2-21 1:1 3.69 105.5 Green 183 Example 69 2:1 3.52 103.2 187 Example 70 3:1 3.44 98.2 190 Example 71 1-56:2-32 1:1 3.28 99.5 Green 178 Example 72 2:1 3.21 99.1 182 Example 73 3:1 3.11 98.2 188 Example 74 1-57:2-11 1:1 3.42 99.1 Green 176 Example 75 2:1 3.37 98.4 185 Example 76 3:1 3.27 97.0 189

As can be seen in Table 13, the compound of Formula 1; And when the compound of Formula 2 is included in the organic material layer of the organic light emitting device, more excellent efficiency and lifespan effects are shown. This result can be expected that an exciplex phenomenon occurs when the two compounds are included at the same time.

The exciplex phenomenon is a phenomenon in which energy of the size of the HOMO level of the donor (p-host) and the LUMO level of the acceptor (n-host) is released through electron exchange between two molecules. When the exciplex between two molecules occurs, Reverse Intersystem Crossing (RISC) occurs, and this can increase the internal quantum efficiency of fluorescence to 100%. When a donor (p-host) with good hole transport ability and an acceptor (n-host) with good electron transport capability are used as the host of the light emitting layer, holes are injected into the p-host and electrons are injected into the n-host. can be lowered, thereby helping to improve the lifespan.

The compound represented by Formula 1 according to the present invention is a compound substituted with deuterium, and the compound of the comparative example corresponds to a compound substituted with hydrogen or other than biscarbazole. Compounds substituted with deuterium, whose atomic mass is twice that of hydrogen, have lower zero-point energy and vibrational energy than compounds combined with hydrogen, resulting in lower ground-state energy and weaker intermolecular interactions, making the thin film an amorphous state. This can improve the lifetime of the device.

Deuterium-substituted compounds have low ground state energy, which improves stability, and high C-D dissociation energy, which improves molecular stability and improves lifespan.

Specifically, when the deuterium-substituted compound 1-51 is applied to an organic light emitting device together with the compound of Formula 2, the operation and lifespan are improved compared to the hydrogen-substituted Comparative Compounds A, B, C, and D due to molecular stability and amorphousness. , and it was possible to facilitate energy transfer to the dopant and improve efficiency by minimizing energy loss due to low vibration energy.

In Comparative Example Compound E of Table 13, deuterium was partially substituted, but unlike biscarbazole, dibenzofuran was substituted at position 3 of carbazole, resulting in low HOMO and low hole stability. Example Compounds and Comparative Example Compounds A and B , C and D have lower efficiency, operation and lifetime.

When comparing the cases of compounds 1-26 and 1-50 in Table 13, all deuterium-substituted compounds 1-50 (structures A to C are deuterium-substituted) can improve efficiency by reducing energy loss with low vibration energy and the lifetime could be improved by lowering the ground-state energy. However, compound 1-26 in which the biscarbazole core (structural formula C) is substituted with deuterium was able to improve the driving voltage by increasing the intermolecular interaction and reducing the intermolecular distance and improving the mobility than the compound 1-50.

When comparing compounds 1-5 and 1-29 of Table 13, 1-29 in which only biscarbazole is deuterium-substituted (only structural formula C is D-substituted) and 1-5 in which only aryl groups are deuterium-substituted (only structural formulas A and B are D-substituted). substitution) is different. When radical cation is generated in carbazole, the 3-position of carbazole is activated to form a dimer, which impairs the efficiency and lifetime of the device. However, compounds 1-29 substituted with deuterium in biscarbazole can effectively stabilize radical cation and effectively improve lifespan, whereas compounds 1-5 substituted with deuterium in biscarbazole do not contribute to stabilizing radical cation of biscarbazole and have a longer lifespan. low was confirmed.

100: substrate
200: anode
300: organic material layer
301: hole injection layer
302: hole transport layer
303: light emitting layer
304: hole blocking layer
305: electron transport layer
306: electron injection layer
400: cathode

Claims (15)

An organic light emitting device comprising a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode,
An organic light emitting device wherein at least one layer of the organic material layer includes a heterocyclic compound represented by Formula 1 below and a heterocyclic compound represented by Formula 2 below:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
X1 to X3 are the same as or different from each other, and each independently N; or CRc, at least one is N;
A is a substituted or unsubstituted C6 to C20 arylene group; Or a substituted or unsubstituted C2 to C20 heteroarylene group,
R1 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; SiRR'R”; or -P(=0)RR';
L1 to L3 are the same as or different from each other and are each independently a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,
Ar1 and Ar2 are the same as or different from each other and are each independently a substituted or unsubstituted C1 to C60 alkyl group; Or a substituted or unsubstituted C6 to C60 aryl group;
Ar3 is a substituted or unsubstituted carbazole group; A substituted or unsubstituted C10 to C60 aryl group; Or a C2 to C60 heteroaryl group containing O or S as a substituted or unsubstituted heterogeneous element,
Wherein R, R', and R" are the same as or different from each other and each independently represents a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 A heteroaryl group of
Wherein Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group;
a1 to a3 are the same as or different from each other and each independently represent an integer of 0 to 4, and when a1 to a3 are 2 or more, the substituents in parentheses are the same as or different from each other,
Formula 1 is a bond of the following Structural Formula A to Structural Formula C,
[Structural Formula A]

[Structural Formula B]

[Structural Formula C]

In the structural formulas A to C,

is a position at which structural formulas A to C are bonded, respectively,
the structural formula A and the structural formula B; Structural Formula C above; Alternatively, the deuterium content of the structural formulas A to C is 50% to 100%. The method according to claim 1, wherein the structural formula A and the structural formula B of the formula (1); Structural Formula C above; Or, the deuterium content of the structural formulas A to C is 100% of the organic light emitting device. The organic light emitting device of claim 1, wherein Ar1 and Ar2 are the same as or different from each other and are each independently a C6 to C20 aryl group unsubstituted or substituted with a C1 to C10 alkyl group. The organic light emitting device of claim 1, wherein A is represented by one of Formulas 3 to 5:
[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,
Y1 is O; or S,

Is the formula (2)

means the position connected to,

Is the formula (2)

means a location connected to The organic light emitting device of claim 1, wherein Ar3 is represented by one of the following Chemical Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,
Ar13 is a substituted or unsubstituted C10 to C60 aryl group,
R21 to R28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
Y is O; or S,
a is an integer from 0 to 3, and when a is 2 or more, the substituents in parentheses are the same as or different from each other. The organic light emitting device of claim 1, wherein Chemical Formula 1 is represented by any one of the following compounds:

The organic light emitting device of claim 1, wherein the heterocyclic compound represented by Formula 2 is represented by any one of the following compounds:

The method according to claim 1, wherein the organic material layer includes at least one layer of a hole blocking layer, an electron injection layer and an electron transport layer, wherein at least one layer of the hole blocking layer, electron injection layer and electron transport layer is a heterocycle represented by Formula 1 An organic light emitting device comprising a compound and a heterocyclic compound represented by Chemical Formula 2. The organic light emitting device of claim 1, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2. The method according to claim 1, wherein the organic material layer includes a light emitting layer, the light emitting layer includes a host material, wherein the host material comprises a heterocyclic compound represented by the formula (1) and a heterocyclic compound represented by the formula (2) phosphorus organic light emitting device. The method according to claim 1, wherein the organic light emitting element is a light emitting layer, a hole injection layer, a hole transport layer. An organic light emitting device further comprising one layer or two or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer. A composition for an organic material layer of an organic light emitting device comprising the heterocyclic compound represented by Chemical Formula 1 according to claim 1 and the heterocyclic compound represented by Chemical Formula 2. The method according to claim 12, wherein the weight ratio of the heterocyclic compound represented by the formula (1): the heterocyclic compound represented by the formula (2) in the composition is 1: 10 to 10: 1 of the composition for an organic layer of an organic light emitting device. Preparing a substrate;
forming a first electrode on the substrate;
forming one or more organic material layers on the first electrode; and
Forming a second electrode on the organic material layer,
The step of forming the organic material layer comprises forming one or more organic material layers using the composition for an organic material layer according to claim 12 . The organic light emitting device of claim 14, wherein the forming of the organic material layer is formed by pre-mixing the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 using a thermal vacuum deposition method. manufacturing method.

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