KR20230083135A - Heterocyclic compound, organic light emitting device comprising the same, composition for organic layer of organic light emitting device and method for manufacturing organic light emitting device - Google Patents

Abstract

The present application relates to a heterocyclic compound capable of significantly improving lifespan, efficiency, electrochemical stability and thermal stability of an organic light emitting device, an organic light emitting device in which the heterocyclic compound is contained in a hole transport layer, and a composition for an organic layer of the organic light emitting device. And it relates to a method of manufacturing the organic light emitting device.

Description

Heterocyclic compound, organic light emitting device including the same, composition for an organic layer of an organic light emitting device, and method for manufacturing an organic light emitting device ORGANIC LIGHT EMITTING DEVICE}

The present specification relates to a heterocyclic compound, an organic light emitting device including the same, 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 application is intended to provide a heterocyclic compound, an organic light emitting device including the same, a composition for an organic material layer of the organic light emitting device, and a manufacturing method of 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, wherein at least one of the organic material layers is represented by Chemical Formula 1 below. It provides an organic light emitting device including a heterocyclic compound represented by and a heterocyclic compound represented by Chemical Formula 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X is O; or S,

R1 is hydrogen; or deuterium;

Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Ar2 and Ar3 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

R2 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

m is an integer from 0 to 4, and when m is 2 or more, Ar2 in parentheses are the same as or different from each other;

n is an integer from 0 to 2, and when n is 2 or more, Ar3 in parentheses are the same as or different from each other;

m+n≥1, and at least one of Ar2 and Ar3 in parentheses is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

a is an integer from 0 to 7, and when a is 2 or more, R2 in parentheses are the same as or different from each other;

Rc and Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; -SiR31R32R33; -P(=0)R31R32; and a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms and a substituted or unsubstituted amine group selected from the group consisting of Or, two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R21 and R22 are the same as or different from each other, and are each independently -(L)k-SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

L is a direct bond; Or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, k is an integer of 0 to 2, and when k is 2, L in parentheses is the same as or different from each other,

R31, R32, and R33 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

r and s are integers from 0 to 7, and when r and s are integers of 2 or greater, the substituents in parentheses are the same as or different from each other.

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

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 the organic material layer. to provide.

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 used as a material for a hole transport layer or an electron blocking 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 used in an organic light emitting device, the driving voltage of the device is lowered, the light efficiency is improved, and the life of the device is increased due to the thermal stability of the compound. characteristics can be improved.

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.

Hereinafter, this application will be described in detail.

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 below. It provides an organic light emitting device including a heterocyclic compound represented by and a heterocyclic compound represented by Chemical Formula 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X is O; or S,

R1 is hydrogen; or deuterium;

Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Ar2 and Ar3 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

R2 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

m is an integer from 0 to 4, and when m is 2 or more, Ar2 in parentheses are the same as or different from each other;

n is an integer from 0 to 2, and when n is 2 or more, Ar3 in parentheses are the same as or different from each other;

m+n≥1, and at least one of Ar2 and Ar3 in parentheses is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

a is an integer from 0 to 7, and when a is 2 or more, R2 in parentheses are the same as or different from each other;

Rc and Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; -SiR31R32R33; -P(=0)R31R32; and a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms and a substituted or unsubstituted amine group selected from the group consisting of Or, two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R21 and R22 are the same as or different from each other, and are each independently -(L)k-SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

L is a direct bond; Or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, k is an integer of 0 to 2, and when k is 2, L in parentheses is the same as or different from each other,

R31, R32, and R33 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

r and s are integers from 0 to 7, and when r and s are integers of 2 or greater, the substituents in parentheses are the same as or different from each other.

Since the molecular structure of the host used in the light emitting layer (EML) of the organic light emitting device must have electron injection/transport characteristics and hole injection/transport characteristics at the same time, it is an essential element to have bipolarity. Since the balance of electrons/holes in these bipolar molecules is quite difficult, recently, p-type molecules with hole characteristics and n-type molecules with electronic characteristics are used to adjust the ratio to control the balance of electrons and holes in the light emitting layer. are doing

When the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are used in an organic light emitting device, performance and lifespan of the device may be increased. In addition, the driving voltage of the device can be lowered and the efficiency of the device can be increased. In particular, when used in the light emitting layer of an organic light emitting device, the device can show more excellent performance.

This result can be expected that an exciplex phenomenon occurs when the two compounds are included at the same time. The exciplex phenomenon is an electron exchange between two molecules, and the HOMO level (highest occupied molecular orbital level) of the donor (donor, p-host function) and the LUMO level (lowest unoccupied molecular orbital level) of the acceptor (acceptor, n-host function) level) is a phenomenon in which energy is released.

When the exciplex between two molecules occurs, RISC (Reverse Intersystem Crossing) occurs, and this can increase the internal quantum efficiency of phosphorescence to 100%.

That is, when a donor with good hole transport ability and an acceptor with good electron transport capability are used as the host of the light emitting layer, the driving voltage can be lowered because holes are injected into the p-host and electrons are injected into the n-host. , thereby helping to improve lifespan.

The heterocyclic compound represented by Chemical Formula 1 has a structure using fluorene as a core, and due to the planar structural characteristics of fluorene, the distance between molecules is closer when stacked on a substrate. Accordingly, intermolecular electron transport becomes smoother, thereby reducing the driving voltage.

In addition, the heterocyclic compound represented by Chemical Formula 1 has relatively low HOMO and LUMO values due to the weaker hole transport ability of fluorene than that of carbazole.

Therefore, hole traps and electron blocking can be reduced when holes and electrons pass from the auxiliary layer to the emission material layer (EML), respectively, and the charge balance of the emission layer (EML) It has the advantage of being easy to match.

In addition, as the heterocyclic compound represented by Formula 1 uses a compound having good hole transport ability, such as the heterocyclic compound represented by Formula 2, the lifespan of the device is improved due to appropriate movement of the light emitting zone in the light emitting layer. there is.

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 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 that it is substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent in which two or more substituents selected from the above exemplified substituents are linked, wherein R, R' and R" are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; substituted or unsubstituted alkyl having 1 to 60 carbon atoms; substituted or unsubstituted aryl having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms.

In the present specification, "Cn" means n number of carbon atoms. That is, C60 means that the number of carbon atoms is 60.

In the present specification, "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) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

In an exemplary embodiment of the present application, "when no substituent is indicated in the chemical formula or compound structure" may mean that all possible positions of the substituent are hydrogen or deuterium. That is, deuterium is an isotope of hydrogen, and some hydrogen atoms may be an isotope of deuterium, and in this case, the content of deuterium may be 0% to 100%.

In one embodiment of the present application, in "when no substituent is indicated in the chemical formula or compound structure", the content of deuterium is 0%, the content of hydrogen is 100%, and all substituents explicitly exclude deuterium such as hydrogen. If not, hydrogen and deuterium may be mixed and used in the compound.

In one embodiment of the present application, 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 2H.

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

로 표시되는 페닐기에 있어 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 경우 20%로 표시될 수 있다. 즉, 페닐기에 있어 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 means that the total number of substituents that the phenyl group can have is 5 (T1 in the formula), and if the number of deuterium is 1 (T2 in the formula), it will be represented as 20% can 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 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, 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 is not limited.

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. The phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, the silyl group includes Si and is a substituent to which the Si atom is directly connected as a radical, 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.

In the present specification, the spiro group is a group including a spiro structure, and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group. Specifically, the following spiro group may include any one of groups of the following structural formula.

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.

In the present specification, "p to q" means more than p and less than q.

The heterocyclic compound represented by Chemical Formula 1 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.

In one embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 1 is 0% or more and 100% or less.

In one embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1 is more than 0% and less than 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 1 is 1% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 1 is 10% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 1 is 20% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 1 is 40% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 1 is 10% to 90%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 1 is 20% to 80%.

When the compound represented by Formula 1 contains deuterium, compared to the case where deuterium is not included, the photochemical characteristics are similar, but when deposited on a thin film, the material containing deuterium packs a narrower intermolecular distance ( packing). Accordingly, compounds containing deuterium exhibit more balanced charge transport characteristics. These characteristics can be confirmed through a method of manufacturing an EOD (Electron Only Device) and a HOD (Hole Only Device) and checking the current density according to the voltage.

In addition, the higher the content of deuterium, that is, the higher the substitution rate of deuterium, the better the performance of the device using the deuterium.

In addition, when only a specific substituent in Formula 1 is partially substituted with deuterium, the substituent corresponding to Ar1 in Formula 1 is substituted with deuterium, rather than a dibenzofuran group, dibenzothiophene group or fluorene in Formula 1 Substitution of deuterium in the portion corresponding to may further improve the performance of the device using the heterocyclic compound represented by Formula 1.

In an exemplary embodiment of the present application, Ar1 in Chemical Formula 1 may be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In an exemplary embodiment of the present application, Ar1 may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In an exemplary embodiment of the present application, Ar1 may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In one embodiment of the present application, Ar1 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or it may be a substituted or unsubstituted terphenyl group.

In an exemplary embodiment of the present application, Ar1 is a phenyl group unsubstituted or substituted with one or more deuterium; A biphenyl group unsubstituted or substituted with one or more deuterium; Or it may be a terphenyl group unsubstituted or substituted with one or more deuterium.

In an exemplary embodiment of the present application, Ar2 and Ar3 of Formula 1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; It may be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, Ar2 and Ar3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; It may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, Ar2 and Ar3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; It may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, Ar2 and Ar3 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 terphenyl group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophene group.

In an exemplary embodiment of the present application, Ar2 and Ar3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with one or more deuterium; A biphenyl group unsubstituted or substituted with one or more deuterium; A terphenyl group unsubstituted or substituted with one or more deuterium; A fluorene group unsubstituted or substituted with one or more selected from the group consisting of heavy hydrogen and an alkyl group having 1 to 20 carbon atoms; A dibenzofuran group unsubstituted or substituted with at least one deuterium; Alternatively, it may be a dibenzothiophene group unsubstituted or substituted with one or more deuterium atoms.

In an exemplary embodiment of the present application, Ar2 and Ar3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with one or more deuterium; A biphenyl group unsubstituted or substituted with one or more deuterium; A terphenyl group unsubstituted or substituted with one or more deuterium; Deuterium, and a fluorene group unsubstituted or substituted with one or more selected from the group consisting of a methyl group; A dibenzofuran group unsubstituted or substituted with one or more deuterium; Alternatively, it may be a dibenzothiophene group unsubstituted or substituted with one or more deuterium atoms.

In an exemplary embodiment of the present application, R2 of Formula 1 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; Or it may be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In an exemplary embodiment of the present application, R2 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 40 carbon atoms; Or it may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In an exemplary embodiment of the present application, R2 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Or it may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present application, R2 is hydrogen; or deuterium.

In an exemplary embodiment of the present application, m is an integer from 0 to 4, and when m is 2 or more, Ar2 in parentheses may be the same as or different from each other.

In one embodiment of the present application, m is 0.

In one embodiment of the present application, m is 1.

In one embodiment of the present application, m is 2.

In one embodiment of the present application, m is 3.

In one embodiment of the present application, m is 4.

In an exemplary embodiment of the present application, when m is 2 or more, Ar2 in parentheses is the same as or different from each other.

In one embodiment of the present application, n is an integer from 0 to 2, and when n is 2 or more, Ar3 in parentheses may be the same as or different from each other.

In one embodiment of the present application, n is 0.

In one embodiment of the present application, n is 1.

In one embodiment of the present application, n is 2.

In an exemplary embodiment of the present application, when n is 2 or more, Ar3 in parentheses is the same as or different from each other.

In one embodiment of the present application, m+n≥1.

In an exemplary embodiment of the present application, m+n≥1, and at least one of Ar2 and Ar3 in parentheses is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms. It is Ki. That is, the fluorene structure of the compound represented by Formula 1 has at least one substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms as a substituent.

In an exemplary embodiment of the present application, m+n≥1, and at least one of Ar2 in parentheses is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, , Ar3 in parentheses is hydrogen; or deuterium.

In an exemplary embodiment of the present application, a is an integer from 0 to 7, and when a is 2 or more, R2 in parentheses may be the same as or different from each other.

In one embodiment of the present application, a is 0.

In one embodiment of the present application, a is 1.

In one embodiment of the present application, a is 2.

In one embodiment of the present application, a is 3.

In one embodiment of the present application, a is 4.

In one embodiment of the present application, a is 5.

In one embodiment of the present application, a is 6.

In one embodiment of the present application, a is 7.

In an exemplary embodiment of the present application, when a is 2 or more, R2 in parentheses is the same as or different from each other.

In an exemplary embodiment of the present application, Formula 1 may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

Ar4 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms;

R3 and R4 are the same as or different from each other, and each independently hydrogen; or deuterium;

b is an integer from 0 to 3;

c is an integer from 0 to 2;

When b and c are each 2 or more, the substituents in parentheses are the same as or different from each other,

The definitions of X, R1, R2, Ar1 and a are the same as in Formula 1.

In an exemplary embodiment of the present application, Ar4 in Chemical Formula 3 may be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In one embodiment of the present application, Ar4 may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, Ar4 may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, Ar4 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophene group.

In an exemplary embodiment of the present application, Ar4 is a phenyl group unsubstituted or substituted with one or more deuterium; A biphenyl group unsubstituted or substituted with one or more deuterium; A terphenyl group unsubstituted or substituted with one or more deuterium; A fluorene group unsubstituted or substituted with one or more selected from the group consisting of heavy hydrogen and an alkyl group having 1 to 20 carbon atoms; A dibenzofuran group unsubstituted or substituted with one or more deuterium; Alternatively, it may be a dibenzothiophene group unsubstituted or substituted with one or more deuterium atoms.

In an exemplary embodiment of the present application, Ar4 is a phenyl group unsubstituted or substituted with one or more deuterium; A biphenyl group unsubstituted or substituted with one or more deuterium; A terphenyl group unsubstituted or substituted with one or more deuterium; Deuterium, and a fluorene group unsubstituted or substituted with one or more selected from the group consisting of a methyl group; A dibenzofuran group unsubstituted or substituted with one or more deuterium; Alternatively, it may be a dibenzothiophene group unsubstituted or substituted with one or more deuterium atoms.

In an exemplary embodiment of the present application, X in Formula 1 is O; or S.

In one embodiment of the present application, the X is O.

In one embodiment of the present application, the X is S.

In an exemplary embodiment of the present application, R1 is deuterium; or hydrogen.

In an exemplary embodiment of the present application, R1 is deuterium.

In an exemplary embodiment of the present application, R1 is hydrogen.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 may be 0% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 may be greater than 10% and less than 100%.

In one embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 2 is 1% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 2 is 10% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 is 20% to 100%.

In one embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 2 is 40% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 2 is 10% to 90%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 is 20% to 80%.

When the compound represented by Formula 2 contains deuterium, compared to the case without deuterium, the photochemical characteristics are similar, but when deposited on a thin film, the material containing deuterium packs a narrower intermolecular distance ( packing). Accordingly, compounds containing deuterium exhibit more balanced charge transport characteristics. These characteristics can be confirmed through a method of manufacturing an EOD (Electron Only Device) and a HOD (Hole Only Device) and checking the current density according to the voltage.

In addition, the higher the content of deuterium, that is, the higher the substitution rate of deuterium, the better the performance of the device using the deuterium. In addition, when partially deuterium is substituted, the case where biscarbazole is deuterium-substituted rather than the aryl group (meaning R16 and R17 in Formula 2) of Formula 2 is deuterium-substituted. The device's performance is better.

According to an exemplary embodiment of the present application, Rc and Rd in Chemical Formula 2 are hydrogen; or deuterium.

In another exemplary embodiment, R21 and R22 in Formula 2 are the same as or different from each other, and each independently -(L)k-SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, R31, R32, and R33 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -(L)k-SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -(L)k-SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -(L)k-SiR31R32R33; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted triphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted spirobifluorene group; A substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophene group.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -(L)k-SiR31R32R33; A triphenylsilyl group, a phenyl group unsubstituted or substituted with at least one selected from the group consisting of deuterium and -CN; A biphenyl group unsubstituted or substituted with heavy hydrogen; A triphenyl group unsubstituted or substituted with heavy hydrogen; A terphenyl group unsubstituted or substituted with heavy hydrogen; A naphthyl group unsubstituted or substituted with heavy hydrogen; A fluorene group unsubstituted or substituted with at least one selected from the group consisting of deuterium, a phenyl group unsubstituted or substituted with deuterium, and a methyl group unsubstituted or substituted with deuterium; A substituted or unsubstituted spirobifluorene group with heavy hydrogen; A dibenzofuran group unsubstituted or substituted with heavy hydrogen; Or it may be a dibenzothiophene group unsubstituted or substituted with deuterium.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -(L)k-SiR31R32R33; A triphenylsilyl group, a phenyl group unsubstituted or substituted with at least one selected from the group consisting of deuterium and -CN; A biphenyl group unsubstituted or substituted with heavy hydrogen; A triphenyl group unsubstituted or substituted with heavy hydrogen; A terphenyl group unsubstituted or substituted with heavy hydrogen; A naphthyl group unsubstituted or substituted with heavy hydrogen; A dimethylfluorene group unsubstituted or substituted with heavy hydrogen; A diphenylfluorene group unsubstituted or substituted with heavy hydrogen; A substituted or unsubstituted spirobifluorene group with heavy hydrogen; A dibenzofuran group unsubstituted or substituted with heavy hydrogen; Or it may be a dibenzothiophene group unsubstituted or substituted with deuterium.

In one embodiment of the present application, the L is a direct bond; or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, k is an integer of 0 to 2, and when k is 2, L in parentheses may be the same as or different from each other.

In one embodiment of the present application, the L is a direct bond; or a substituted or unsubstituted arylene group having 6 to 40 carbon atoms.

In one embodiment of the present application, the L is a direct bond; or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

In one embodiment of the present application, the L is a direct bond; Or a substituted or unsubstituted phenylene group.

In one embodiment of the present application, k is 0.

In one embodiment of the present application, k is 1.

In an exemplary embodiment of the present application, k is 2.

In one embodiment of the present application, when k is 2, L in parentheses is the same as or different from each other.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently may be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently may be a phenyl group unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present application, r and s are integers from 0 to 7, and when r and s are integers of 2 or more, substituents in parentheses may be the same as or different from each other.

In an exemplary embodiment of the present application, r may be 0, 1, 2, 3, 4, 5, 6 or 7. When r is an integer of 2 or more, the substituents in parentheses may be the same as or different from each other.

In one embodiment of the present application, s may be 0, 1, 2, 3, 4, 5, 6 or 7. When s is an integer of 2 or more, the substituents in parentheses may be the same as or different from each other.

In the present specification, the -(L)k-SiR31R32R33 means the same form as the following formula (L).

[Formula L]

In the formula L,

The definitions of L, k and R31 to R33 are as defined in Formula 2, and * represents a position where Formula L is bonded to Formula 2.

According to an exemplary embodiment of the present application, Formula 1 may be represented by any one of the following compounds, but is not limited thereto.

According to an exemplary embodiment of the present application, Formula 2 may be represented by any one of the following compounds, but is not limited thereto.

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 Chemical Formulas 1 and 2, it is possible to finely control the energy band gap, and on the other hand, it is possible to improve the properties at the interface between organic materials and to diversify the use of materials. there is.

Meanwhile, the heterocyclic compounds of Chemical Formulas 1 and 2 have high glass transition temperatures (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 Formulas 1 and 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.

Another exemplary embodiment of the present application provides an organic light emitting device including the heterocyclic compounds represented by Chemical Formulas 1 and 2 above. The "organic light emitting device" may be expressed in terms such as "organic light emitting diode", "organic light emitting diodes (OLED)", "OLED device", and "organic electroluminescent device".

The heterocyclic compound 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 light emitting device of the present invention may further include one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole auxiliary layer, and a hole blocking layer.

The organic material layer includes one or more light emitting layers, and the light emitting layer includes the heterocyclic compounds represented by Chemical Formulas 1 and 2 above. Among the organic material layers, when the light emitting layer includes the heterocyclic compound represented by Chemical Formula 1, the light emitting efficiency and lifetime of the organic light emitting device are more excellent.

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 compound represented by Formula 2 at the same time.

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.

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

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

In an exemplary embodiment of the present application, the organic light emitting device is a green organic light emitting device. That is, a green 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 one embodiment of the present application, a phosphorescent material may be used as the light emitting material.

In one embodiment of the present application, the forming of the organic material layer is performed by supplying the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 to individual sources, and then using a thermal vacuum deposition method. It provides a method of manufacturing an organic light emitting device that is formed.

In an exemplary embodiment of the present application, the forming of the organic material layer is performed by pre-mixing the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 using a thermal vacuum deposition method. It provides a method for manufacturing an organic light emitting device that is to do.

The pre-mixing means that the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are first mixed and mixed in one park before depositing the compound represented by Chemical Formula 2 on the organic material layer.

When depositing through pre-mixing, it is possible to improve the uniformity and characteristics of thin films because multiple depositions are not performed, simplifying the process, reducing costs, and improving efficiency and lifespan. can form

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

An organic light emitting device according to an exemplary embodiment of the present application may be manufactured by a conventional organic light emitting device manufacturing method and material, except for forming an organic material layer using the aforementioned heterocyclic compound.

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

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.

As the light emitting material of the organic light emitting device of the present application, additional red, green or blue light emitting materials may be used within a range that does not significantly affect the performance of the organic light emitting device according to the present invention. If necessary, two or more light emitting materials may be used. Can be used in combination. In addition, a phosphorescent material may be used as the light emitting material, but a fluorescent material may be used as an additional light emitting material within a range that does not significantly affect the performance of the organic light emitting device according to the present invention. In addition, as the light emitting material, a material that emits light by combining holes and electrons injected from an anode and a cathode may be used, but materials in which a host material and a dopant material are involved in light emission may also be used.

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.

[Preparation Example 1] Preparation of compound 1-1

1) Preparation of compound 1-1-1

1-bromo-8-chloro-9,9-dimethyl-9H-fluorene was added to a one neck round bottom flask. ) [A] (6g, 0.020mol), phenylboronic acid [B] (2.62g, 0.021mol), Pd(PPh ₃ ) ₄ (1.16g, 0.001mol), K ₂ CO ₃ (5.53g , 0.040 mol) and 1,4-dioxane/water (60ml/18ml) mixture was refluxed at 120°C for 4 hours. When the reaction was completed, it was quenched and extracted with dichloromethane (DMC) and H ₂ O, concentrated, and then filtered with silica gel. After concentration, it was treated with methanol (Methanol, MeOH) to obtain compound 1-1-1. (5.36g, 88%)

2) Preparation of compound 1-1-2

1-chloro-9,9-dimethyl-8-phenyl-9H-fluorene was added to a one neck round bottom flask. (5.36g, 0.018mol), Bis(pinacolato)diboron (9.14g, 0.036mol), Pd ₂ (dba) ₃ (1.65g, 0.0018mol), Sphos (1.48g, A mixture of 0.0036 mol), potassium acetate (3.53 g, 0.036 mol) and 1,4-dioxane (50 mL) was refluxed at 120 °C. After cooling, the mixture was concentrated and filtered through silica gel to obtain compound 1-1-2. (7.00g, 98%)

3) Preparation of compound 1-1 [D]

2-(9,9-dimethyl-8-phenyl-9H-fluoren-1-yl)-4,4,5,5-tetramethyl-1,3 was added to a one neck round bottom flask. ,2-dioxaborolane (2-(9,9-dimethyl-8-phenyl-9H-fluoren-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (7.00 g, 0.018 mol), 2-chloro-4- (dibenzo [b, d] furan-4-yl) -6-phenyl-1,3,5-triazine (2-chloro-4- (dibenzo [b ,d]furan-4-yl)-6-phenyl-1,3,5-triazine) [C] (12.88 g, 0.036 mol), Pd(PPh ₃ ) ₄ (1.04 g, 0.0009 mol), K ₂ CO A mixture of ₃ (4.98 g, 0.036 mol) and 1,4-dioxane/water (70 mL/21 mL) was refluxed at 120°C. After cooling, the mixture was concentrated and filtered through silica gel to obtain compound 1-1 [D]. (8.41g, 79%)

In Preparation Example 1, 1-bromo-8-chloro-9,9-dimethyl-9H-fluorene (1-bromo-8-chloro-9,9-dimethyl-9H-fluorene) [A], phenylboronic acid (phenylboronic acid) [B] and 2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-phenyl-1,3,5-triazine [b,d]furan-4-yl)-6-phenyl-1,3,5-triazine) Same as in Preparation Example 1 except for using Intermediates A, B, and C in Table 1 below, respectively, instead of [C] Compound D of Table 1 was synthesized by the method.

[Preparation Example 2] Preparation of compound 1-61

1) Preparation of Compound 1-1

Compound 1-1 was prepared in the same manner as in Preparation Example 1.

2) Preparation of compound 1-61 [E]

Compound 1-1 (8.41 g, 0.014 mol), Triflic acid (10.51 g, 0.07 mol) and D ₆ -Benzene were added to _a one neck round bottom flask. (80 mL) The mixture was refluxed at 40 °C. After quenching and extracting with DMC and H ₂ O and concentrating, a silica gel filter was applied. This was concentrated and then treated with methanol to obtain 1-61[E]. (8.52 g, yield 98%)

In Preparation Example 1, 1-bromo-8-chloro-9,9-dimethyl-9H-fluorene (1-bromo-8-chloro-9,9-dimethyl-9H-fluorene) [A], phenylboronic acid (phenylboronic acid) [B] and 2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-phenyl-1,3,5-triazine [b,d]furan-4-yl)-6-phenyl-1,3,5-triazine) Except for using intermediates A, B, and C in Table 2 below, respectively, instead of [C], Preparation Example 2 Compound E of Table 2 was synthesized in the same manner as above.

[Preparation Example 3] Preparation of compound 2-23[F]

1) Preparation of compound 2-23 [F]

9-([1,1'-biphenyl]-2-yl)-9H,9'H-3,3'-bicarbazole (9-([ 1,1'-biphenyl]-2-yl)-9H,9'H-3,3'-bicarbazole) [A] (10 g, 0.021 mol), 4-bromo-1,1':4',1 ''-terphenyl (4-bromo-1,1': 4',1''-terphenyl) [B] (7.14 g, 0.023 mol), CuI (0.40 g, 0.0021 mol), trans-1,4- After dissolving trans-1,4-diaminocyclohexane (0.024g, 0.0021mol) and K ₃ PO ₄ (8.92g, 0.042mol) in 100mL of 1,4-dioxane, it was 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. Thereafter, the reactant was purified by column chromatography (DCM:Hex=1:3) and recrystallized from methanol to obtain compound 2-23[F]. (13.02g, 87%)

In Preparation Example 3 -([1,1'-biphenyl]-2-yl)-9H,9'H-3,3'-bicarbazole (9-([1,1'-biphenyl]-2 -yl) -9H,9'H-3,3'-bicarbazole) [A] (10 g, 0.021 mol) and 4-bromo-1,1':4',1''-terphenyl (4-bromo Compound F in Table 3 was synthesized in the same manner as in Preparation Example 3, except that intermediates A and B in Table 3 were used instead of -1,1': 4', 1''-terphenyl) [B]. .

Compounds were prepared in the same manner as in the above preparations, and the synthesis confirmation results are shown in Tables 4 and 5 below. Specifically, Table 4 is a measurement value of ¹ H NMR (CDCl ₃ , 300 Mz), and Table 5 is a measurement value of FD-mass spectrometer (FD-MS: Field desorption mass spectrometry).

compound ¹ H NMR (DMSO, 300 Mz) 1-1 δ = 8.36 (2H, m), 8.08 (1H, d), 8.00 (2H, m), 7.88 (1H, d), 7.68 (2H, d), 7.31~7.57 (14H, m), 1.69 (6H, s) 1-4 δ = 8.36 (2H, m), 7.98 to 8.00 (3H, m), 7.82 (1H, d), 7.68 to 7.69 (3H, m), 7.31 to 7.57 (14H, m), 1.69 (6H, s) 1-5 δ = 8.08 (1H, d), 7.96 to 8.00 (5H, m), 7.88 (1H, d), 7.68 to 7.75 (4H, m), 7.25 to 7.57 (16H, m), 1.69 (6H, s) 1-8 δ = 7.96~8.00 (5H, m), 7.68~7.82 (6H, m), 7.25~7.57 (16H, m), 1.69 (6H, s) 1-9 δ = 8.38 (1H, d), 8.08 (1H, d), 7.88 to 8.00 (5H, m), 7.31 to 7.75 (20H, m), 1.69 (6H, s) 1-14 δ = 7.94~7.98 (4H, m), 7.31~7.75 (22H, m), 1.69 (6H, s) 1-18 δ = 7.96~8.03 (6H, m), 7.68~7.82 (6H, m), 7.68~7.82 (6H, m), 7.25~7.57 (19H, m), 1.69 (6H, s) 1-21 δ = 8.36 (2H, m), 8.08 (1H, d), 7.98 to 8.00 (3H, m), 7.88 (1H, d), 7.68 to 7.75 (4H, m), 7.25 to 7.57 (16H, m), 1.69 (6H, s) 1-27 δ = 7.25~8.00 (31H, m), 1.69 (6H, s) 1-30 δ = 8.38 (1H, d), 7.94~8.03 (5H, m), 7.25~7.82 (25H, m), 1.69 (6H, s) 1-41 δ = 8.36 (2H, m), 7.98 to 8.08 (7H, m), 7.88 (1H, d), 7.68 (2H, d), 7.50 to 7.57 (9H, m), 7.31 to 7.39 (4H, m), 1.69 (6H, s) 1-42 δ = 8.36 (2H, m), 7.98 to 8.03 (6H, m), 7.76 to 7.82 (4H, m), 7.68 (2H, d), 7.50 to 7.57 (7H, m), 7.31 to 7.39 (4H, m) ), 1.69 (6H, s) 1-47 δ = 7.75 to 8.03 (7H, m), 7.75 to 7.88 (9H, m), 7.25 to 7.57 (13H, m), 1.69 (6H, s) 1-49 δ = 8.55 (1H, d), 8.32~8.45 (3H, m), 8.08 (1H, d), 7.88~8.00 (6H, m), 7.31~7.75 (18H, m), 1.69 (6H, s) 1-61 δ = no ¹ H NMR peak with 100% deuterium content 1-64 δ = no ¹ H NMR peak with 100% deuterium content 1-69 δ = no ¹ H NMR peak with 100% deuterium content 1-72 δ = no ¹ H NMR peak with 100% deuterium content 1-73 δ = 8.55 (1H, d), 8.45 (1H, d), 8.36 (2H, m), 7.92 to 8.00 (4H, m), 7.68 to 7.70 (3H, m), 7.38 to 7.57 (12H, m), 1.69 (6H, s) 1-78 δ = 8.45 (1H, d), 8.20 to 8.24 (2H, m), 7.93 to 8.00 (6H, m), 7.68 to 7.75 (4H, m), 7.38 to 7.57 (12H, m), 7.25 (2H, d ), 1.69 (6H, s) 1-80 δ = 8.45 (1H, d), 7.93–8.03 (7H, m), 7.68–7.75 (5H, m), 7.38–7.57 (12H, m), 7.25 (2H, d), 1.69 (6H, s) 1-81 δ = 8.55 (1H, d), 8.38 to 8.45 (2H, m), 7.93 to 8.00 (5H, m), 7.38 to 7.75 (19H, m), 1.69 (6H, s) 1-86 δ = 8.45 (1H, d), 8.20 to 8.24 (2H, m), 7.93 to 8.00 (7H, m), 7.38 to 7.75 (19H, m), 7.25 (2H, d), 1.69 (6H, s) 1-90 δ = 8.45 (1H, d), 8.20 to 8.24 (2H, m), 7.93 to 8.00 (6H, m), 7.68 to 7.75 (4H, m), 7.38 to 7.57 (12H, m), 7.25 (6H, m) ), 1.69 (6H, s) 1-94 δ = 8.45 (1H, d), 8.36 (2H, m), 8.20 to 8.24 (2H, m), 7.93 to 8.00 (4H, m), 7.68 to 7.75 (4H, m), 7.41 to 7.57 (10H, m) ), 7.25 (4H, s), 1.69 (6H, s) 1-100 δ = 8.45 (1H, d), 7.93 to 8.03 (8H, m), 7.41 to 7.75 (20H, m), 7.25 (2H, d), 1.69 (6H, s) 1-113 δ = 8.55 (1H, d), 8.45 (1H, d), 8.36 (2H, m), 7.92 to 8.08 (7H, m), 7.68 to 7.70 (3H, m), 7.49 to 7.57 (9H, m), 7.31~7.39 (2H, m), 1.69 (6H, s) 1-118 δ = 8.45 (1H, d), 8.20 to 8.24 (2H, m), 7.93 to 8.08 (9H, m), 7.68 to 7.75 (4H, m), 7.25 to 7.57 (13H, m), 1.69 (6H, s ) 1-124 δ = 8.55 (1H, d), 8.32–8.45 (4H, m), 7.93–8.03 (7H, m), 7.41–7.75 (17H, m), 1.69 (6H, s) 1-133 δ = no ¹ H NMR peak with 100% deuterium content 1-136 δ = no ¹ H NMR peak with 100% deuterium content 1-140 δ = no ¹ H NMR peak with 100% deuterium content 1-144 δ = no ¹ H NMR peak with 100% deuterium content 1-145 δ = 8.36 (2H, m), 8.08 to 8.09 (2H, d), 8.00 (1H, m), 7.88 to 7.89 (2H, m), 7.68 to 7.75 (4H, m), 7.31 to 7.57 (10H, m) ), 1.69 (6H, s) 1-146 δ = 8.36 (2H, m), 7.98 to 8.09 (4H, m), 7.89 (1H, s), 7.68 to 7.82 (6H, m), 7.31 to 7.57 (10H, m), 1.69 (6H, s) 1-148 δ = 8.36 (2H, m), 8.09 (1H, d), 7.98 to 8.00 (2H, m), 7.89 (1H, s), 7.68 to 7.82 (6H, m), 7.31 to 7.57 (11H, m), 1.69 (6H, s) 1-150 δ = 7.96~8.09 (6H, m), 7.89 (1H, s), 7.75~7.82 (8H, m), 7.25~7.57 (12H, m), 1.69 (6H, s) 1-154 δ = 8.38 (1H, d), 7.89 to 8.09 (6H, m), 7.31 to 7.82 (20H, m), 1.69 (6H, s) 1-160 δ = 8.09 (1H, d), 7.89 to 8.00 (6H, m), 7.25 to 7.78 (24H, m), 1.69 (6H, s) 1-161 δ = 8.08~8.09 (2H, m), 7.96~8.00 (4H, m), 7.88~7.89 (2H, m), 7.68~7.78 (6H, m), 7.25~7.57 (17H, m), 1.69 (6H) , s) 1-166 δ = 8.36 (2H, m), 7.98 to 8.09 (4H, m), 7.89 (1H, s), 7.75 to 7.82 (6H, m), 7.14 to 7.54 (14H, m), 1.69 (6H, s) 1-171 δ = 8.09 (1H, d), 7.25~8.00 (35H, m), 1.69 (6H, s) 1-176 δ = 8.38 (1H, d), 8.09 (1H, d), 7.89 to 8.00 (5H, m), 7.31 to 7.82 (24H, m), 1.69 (6H, s) 1-189 δ = 7.96~8.09 (8H, m), 7.68~7.89 (8H, m), 7.25~7.57 (13H, m), 1.69 (6H, s) 1-190 δ = 7.96~8.09 (9H, m), 7.89 (1H, s), 7.68~7.82 (6H, m), 7.25~7.57 (13H, m), 1.69 (6H, s) 1-192 δ = 7.96~8.09 (8H, m), 7.89 (1H, s), 7.69~7.82 (6H, m), 7.25~7.57 (14H, m), 1.69 (6H, s) 1-193 δ = 8.55 (1H, d), 8.32~8.38 (3H, m), 8.08~8.09 (2H, m), 7.88~8.00 (6H, m), 7.31~7.78 (17H, m), 1.69 (6H, s) ) 1-198 δ = 8.45 (1H, d), 7.93~8.12 (12H, m), 7.25~7.82 (20H, m), 1.69 (6H, s) 1-205 δ = no ¹ H NMR peak with 100% deuterium content 1-212 δ = no ¹ H NMR peak with 100% deuterium content 1-215 δ = no ¹ H NMR peak with 100% deuterium content 1-216 δ = no ¹ H NMR peak with 100% deuterium content 1-217 δ = 8.55 (1H, d), 8.45 (1H, d), 8.36 (2H, m), 8.09 (1H, d), 7.89 to 8.00 (4H, m), 7.68 to 7.78 (5H, m), 7.41 to 7.57 (9H, m), 1.69 (6H, s) 1-221 δ = 8.55 (1H, d), 8.45 (1H, d), 8.09 (1H, d), 7.89 to 8.00 (6H, m), 7.68 to 7.78 (7H, m), 7.41 to 7.57 (9H, m), 7.25 (2H, d), 1.69 (6H, s) 1-222 δ = 8.45 (1H, d), 8.20 to 8.24 (2H, m), 8.09 (1H, d), 7.89 to 7.96 (6H, m), 7.68 to 7.78 (6H, m), 7.41 to 7.57 (9H, m) ), 7.25 (2H, d), 1.69 (6H, s) 1-232 δ = 8.45 (1H, d), 7.94 to 8.09 (9H, m), 7.41 to 7.78 (1H, m), 7.25 (2H, d), 1.69 (6H, s) 1-236 δ = 8.45 (1H, d), 7.89 to 8.09 (8H, m), 7.68 to 7.75 (7H, m), 7.41 to 7.57 (9H, m), 7.25 (6H, m), 1.69 (6H, s) 1-239 δ = 8.45 (1H, d), 8.36 (2H, m), 8.09 to 8.12 (2H, m), 7.89 to 8.00 (5H, m), 7.68 to 7.78 (4H, m), 7.41 to 7.57 (9H, m) ), 7.25 (4H, s), 1.69 (6H, s) 1-244 δ = 8.45 (1H, d), 7.89–8.09 (9H, m), 7.41–7.78 (19H, m), 7.25 (2H, d), 1.69 (6H, s) 1-257 δ = 8.55 (1H, d), 8.45 (1H, d), 8.36 (2H, m), 7.89 to 8.09 (8H, m), 7.68 to 7.78 (3H, m), 7.49 to 7.57 (8H, m), 7.31~7.39 (2H, m), 1.69 (6H, s) 1-262 δ = 8.45 (1H, d), 8.20 to 8.24 (2H, m), 7.93 to 8.09 (10H, m), 7.75 to 7.78 (4H, m), 7.31 to 7.56 (12H, m), 1.69 (6H, s ) 1-268 δ = 8.55 (1H, d), 8.32–8.45 (4H, m), 7.89–8.09 (8H, m), 7.41–7.78 (16H, m),. 1.69 (6H, s) 1-277 δ = no ¹ H NMR peak with 100% deuterium content 1-278 δ = no ¹ H NMR peak with 100% deuterium content 1-280 δ = no ¹ H NMR peak with 100% deuterium content 1-283 δ = no ¹ H NMR peak with 100% deuterium content 1-287 δ = no ¹ H NMR peak with 100% deuterium content 1-289 δ = 8.36 (2H, m), 8.18 (1H, s), 8.08 (1H, d), 7.98 to 8.00 (2H, m), 7.88 (1H, d), 7.68 to 7.75 (5H, m), 7.31 to 7.54 (11H, m), 1.69 (6H, s) 1-294 δ = 8.18 (1H, s), 7.96 to 8.03 (5H, m), 7.68 to 7.82 (9H, m), 7.21 to 7.57 (12H, m), 1.69 (6H, s) 1-296 δ = 8.18 (1H, s), 7.96 to 8.00 (4H, m), 7.68 to 7.82 (9H, m), 7.25 to 7.57 (13H, m), 1.69 (6H, s) 1-300 δ = 8.38 (1H, d), 8.18 (1H, s), 7.94 to 8.00 (3H, m), 7.31 to 7.82 (22H, m), 1.69 (6H, s) 1-304 δ = 8.18 (1H, s), 7.94 to 8.00 (5H, m), 7.25 to 7.82 (25H, m), 1.69 (6H, s) 1-311 δ = 8.36 (2H, m), 8.18 (1H, s), 7.98 to 8.00 (2H, m), 7.68 to 7.88 (8H, m), 7.25 to 7.57 (14H, m), 1.69 (6H, s) 1-313 δ = 8.18 (1H, s), 8.08 (1H, d), 7.88 to 7.98 (6H, m), 7.25 to 7.75 (23H, m), 1.69 (6H, s) 1-329 δ = 8.36 (2H, m), 8.18 (1H, s), 7.98 to 8.08 (6H, m), 7.88 (1H, d), 7.68 to 7.74 (3H, m), 7.50 to 7.57 (8H, m), 7.31~7.39 (4H, m), 1.69 (6H, s) 1-334 δ = 8.18 (1H, s), 7.96 to 8.08 (8H, m), 7.68 to 7.82 (7H, m), 7.25 to 7.54 (13H, m), 1.69 (6H, s) 1-340 δ = 8.55 (1H, d), 8.32~8.45 (3H, m), 8.18 (1H, s), 7.93~8.00 (4H, m), 7.31~7.82 (20H, m), 1.69 (6H, s) 1-349 δ = no ¹ H NMR peak with 100% deuterium content 1-356 δ = no ¹ H NMR peak with 100% deuterium content 1-360 δ = no ¹ H NMR peak with 100% deuterium content 1-361 δ = 8.55 (1H, d), 8.45 (1H, d), 8.36 (2H, m), 8.18 (1H, s), 7.92 to 8.00 (3H, m), 7.68 to 7.75 (6H, m), 7.41 to 7.57 (9H, m), 1.69 (6H, s) 1-365 δ = 8.55 (1H, d), 8.45 (1H, d), 8.18 (1H, s), 7.92 to 7.96 (4H, m), 7.68 to 7.75 (8H, m), 7.41 to 7.57 (9H, m), 7.25 (2H, d), 1.69 (6H, s) 1-368 δ = 8.45 (1H, d), 8.18 (1H, s), 7.93 to 8.03 (6H, m), 7.68 to 7.75 (8H, m), 7.41 to 7.57 (9H, m), 7.25 (2H, d), 1.69 (6H, s) 1-374 δ = 8.45 (1H, d), 8.18 to 8.24 (3H, m), 7.93 to 8.00 (6H, m), 7.41 to 7.75 (19H, m), 7.25 (2H, d), 1.69 (6H, s) 1-382 δ = 8.45 (1H, d), 8.36 (2H, m), 8.20 to 8.24 (2H, m), 7.93 to 8.00 (3H, m), 7.68 to 7.75 (5H, m), 7.41 to 7.57 (9H, m) ), 7.25 (4H, s), 1.69 (6H, s) 1-384 δ = 8.45 (1H, s), 8.36 (2H, m), 8.18 (1H, s), 7.93 to 8.03 (4H, m), 7.68 to 7.75 (6H, m), 7.41 to 7.57 (9H, m), 7.25 (4H, s), 1.69 (6H, s) 1-388 δ = 8.45 (1H, d), 8.18 (1H, s), 7.93 to 8.03 (7H, m), 7.41 to 7.75 (20H, m), 7.25 (2H, d), 1.69 (6H, s) 1-401 δ = 8.55 (1H, d), 8.45 (1H, d), 8.36 (2H, m), 8.18 (1H, s), 7.92 to 8.08 (6H, m), 7.68 to 7.74 (4H, m), 7.49 to 7.57 (8H, m), 7.31~7.39 (2H, m), 1.69 (6H, s) 1-407 δ = 8.45 (1H, d), 8.18 (1H, s), 8.12 (1H, s), 7.92 to 8.00 (6H, m), 7.68 to 7.82 (7H, m), 7.25 to 7.57 (11H, m), 1.69 (6H, s) 1-411 δ = 8.38 to 8.45 (3H, m), 8.12 to 8.24 (5H, m), 7.92 to 8.00 (6H, m), 7.41 to 7.75 (15H, m), 1.69 (6H, s) 1-422 δ = no ¹ H NMR peak with 100% deuterium content 1-426 δ = no ¹ H NMR peak with 100% deuterium content 1-432 δ = no ¹ H NMR peak with 100% deuterium content 1-433 δ = 8.36 (2H, m), 8.08 (1H, d), 7.98 to 8.00 (2H, m), 7.88 (1H, d), 7.78 to 7.79 (3H, m), 7.65 to 7.68 (2H, m), 7.31~7.54 (12H, m), 1.69 (6H, s) 1-437 δ = 8.08 (1H, d), 7.96 to 8.00 (4H, m), 7.88 (1H, d), 7.65 to 7.79 (7H, m), 7.25 to 7.57 (14H, m), 1.69 (6H, s) 1-448 δ = 7.94~8.00 (5H, m), 7.25~7.82 (26H, m), 1.69 (6H, s) 1-456 δ = 8.36 (2H, m), 7.98 to 8.00 (2H, m), 7.25 to 7.82 (20H, m), 1.69 (6H, s) 1-474 δ = 8.36 (2H, m), 7.98 to 8.03 (5H, m), 7.76 to 7.82 (5H, m), 7.65 to 7.68 (2H, m), 7.31 to 7.57 (11H, m), 1.69 (6H, s ) 1-478 δ = 7.96~8.03 (8H, m), 7.75~7.82 (6H, m), 7.25~7.57 (12H, m), 1.96 (6H, s) 1-480 δ = 7.96~8.08 (7H, m), 7.25~7.82 (22H, m), 1.69 (6H, s) 1-493 δ = no ¹ H NMR peak with 100% deuterium content 1-495 δ = no ¹ H NMR peak with 100% deuterium content 1-498 δ = no ¹ H NMR peak with 100% deuterium content 1-510 δ = 8.45 (1H, d), 8.20 to 8.24 (2H, m), 7.93 to 8.00 (5H, m), 7.68 to 7.79 (7H, m), 7.41 to 7.57 (10H, m), 7.25 (2H, d ), 1.69 (6H, s) 1-512 δ = 8.45 (1H, d), 7.93 to 8.03 (6H, m), 7.41 to 7.79 (18H, m), 7.25 (2H, d), 1.69 (6H, s) 1-520 δ = 8.45 (1H, d), 7.93 to 8.03 (7H, m), 7.41 to 7.79 (23H, m), 7.25 (2H, d), 1.69 (6H, s) 1-532 δ = 8.45 (1H, d), 7.93 to 8.03 (7H, m), 7.41 to 7.75 (21H, m), 7.25 (2H, d), 1.69 (6H, s) 1-534 δ = 8.38 to 8.45 (2H, m), 8.20 to 8.24 (2H, m), 7.93 to 8.00 (4H, m), 7.41 to 7.78 (19H, m), 7.25 (4H, s), 1.69 (6H, s) ) 1-546 δ = 8.45 (1H, d), 8.36 (2H, m), 8.20 to 8.24 (2H, m), 7.94 to 8.03 (4H, m), 7.76 to 7.78 (3H, m), 7.65 to 7.68 (2H, m) ), 7.31~7.57 (10H, m), 1.69 (6H, s) 1-551 δ = 8.45 (1H, d), 8.12 (1H, s), 7.92 to 8.03 (8H, m), 7.65 to 7.82 (7H, m), 7.25 to 7.57 (12H, m), 1.69 (6H, s) 1-555 δ = 8.38 to 8.45 (3H, m), 8.12 to 8.24 (4H, m), 7.92 to 8.00 (6H, m), 7.41 to 7.78 (16H, m), 1.69 (6H, s) 1-560 δ = 8.45 (1H, d), 8.17 to 8.24 (3H, m), 7.93 to 8.03 (8H, m), 7.41 to 7.75 (20H, m), 7.25 (2H, d), 1.69 (6H, s) 1-568 δ = no ¹ H NMR peak with 100% deuterium content 1-570 δ = no ¹ H NMR peak with 100% deuterium content 1-574 δ = no ¹ H NMR peak with 100% deuterium content 1-577 δ = 8.36 (2H, m), 8.08 to 8.09 (2H, m), 7.98 to 8.00 (2H, m), 7.88 (1H, d), 7.78 (1H, d), 7.68 (1H, d), 7.31 to 7.57 (13H, m), 1.69 (6H, s) 1-580 δ = 8.36 (2H, m), 8.09 (1H, d), 7.98 to 8.00 (2H, m), 7.89 (1H, s), 7.78 to 7.82 (2H, m), 7.68 to 7.69 (2H, m), 7.31~7.57 (13H, m), 1.69 (6H, s) 1-583 δ = 8.09 (1H, d), 7.96 to 8.00 (4H, m), 7.68 to 7.89 (8H, m), 7.25 to 7.57 (14H, m), 1.69 (6H, s) 1-598 δ = 8.36 (2H, m), 7.98 to 8.09 (4H, m), 7.89 (1H, s), 7.68 to 7.82 (6H, m), 7.25 to 7.57 (14H, m), 1.69 (6H, s) 1-600 δ = 8.36 (2H, m), 8.09 (1H, d), 7.98 to 8.00 (2H, m), 7.89 (1H, s), 7.68 to 7.82 (6H, m), 7.25 to 7.57 (15H, m), 1.69 (6H, s) 1-617 δ = 8.36 (2H, m), 7.98 to 8.09 (7H, m), 7.88 to 7.89 (2H, d), 7.78 (1H, d), 7.68 (1H, d), 7.50 to 7.57 (8H, m), 7.31~7.39 (4H, m), 1.69 (6H, s) 1-620 δ = 8.36 (2H, m), 7.98 to 8.09 (5H, m), 7.89 (1H, s), 7.76 to 7.82 (4H, m), 7.68 to 7.69 (2H, m), 7.50 to 7.57 (7H, m) ), 7.31~7.39 (4H, m), 1.69 (6H, s) 1-623 δ = 7.96~8.09 (7H, m), 7.68~7.88 (10H, m), 7.25~7.55 (12H, m), 1.69 (6H, s) 1-628 δ = 8.55 (1H, d), 8.32~8.45 (3H, m), 8.09 (1H, d), 7.89~8.00 (5H, m), 7.31~7.82 (19H, m), 1.69 (6H, s) 1-637 δ = no ¹ H NMR peak with 100% deuterium content 1-642 δ = no ¹ H NMR peak with 100% deuterium content 1-644 δ = no ¹ H NMR peak with 100% deuterium content 1-647 δ = no ¹ H NMR peak with 100% deuterium content 1-653 δ = 8.55 (1H, d), 8.45 (1H, d), 8.09 (1H, d), 7.89 to 8.00 (6H, m), 7.68 to 7.78 (5H, m), 7.38 to 7.57 (11H, m), 7.25 (2H, d), 1.69 (6H, s) 1-655 δ = 8.45 (1H, d), 8.09 to 8.12 (2H, m), 7.89 to 8.00 (7h, m), 7.68 to 7.78 (4H, m), 7.38 to 7.57 (11H, m), 7.25 (2H, d ), 1.69 (6H, s) 1-659 δ = 8.38~8.45 (2H, m), 8.09~8.12 (2H, m), 7.92~8.00 (5H, m), 7.38~7.75 (17H, m), 1.69 (6H, s) 1-670 δ = 8.45 (1H, d), 8.36 (2H, m), 8.20 to 8.24 (2H, m), 8.09 (1H, d), 7.93 to 8.00 (4H, m), 7.68 to 7.78 (4H, m), 7.41 to 7.57 (9H, m), 7.25 (4H, s), 1.69 (6H, s) 1-690 δ = 8.45 (1H, d), 8.36 (2H, m), 8.20 to 8.24 (2H, m), 7.89 to 8.09 (7H, m), 7.76 to 7.82 (3H, m), 7.68 (1H, d), 7.49~7.57 (7H, m), 7.31~7.39 (2H, m), 1.69 (6H, s) 1-692 δ = 8.45 (1H, d), 8.36 (2H, m), 7.89 to 8.09 (8H, m), 7.76 to 7.82 (3H, m), 7.68 (2H, m), 7.49 to 7.57 (6H, m), 7.31~7.39 (2H, m), 1.69 (6H, s) 1-693 δ = 8.55 (1H, d), 8.45 (1H, d), 7.89 to 8.09 (9H, m), 7.68 to 7.82 (7H, m), 7.25 to 7.56 (11H, m), 1.69 (6H, s) 1-699 δ = 8.38~8.45 (3H, m), 8.09~8.24 (5H, m), 7.89~7.99 (7H, m), 7.49~7.75 (14H, m), 1.69 (6H, s) 1-710 δ = no ¹ H NMR peak with 100% deuterium content 1-713 δ = no ¹ H NMR peak with 100% deuterium content 1-718 δ = no ¹ H NMR peak with 100% deuterium content 1-721 δ = 8.36 (2H, m), 8.08 to 8.09 (3H, m), 7.98 (1H, d), 7.88 to 7.89 (3H, m), 7.75 to 7.78 (4H, m), 7.31 to 7.54 (10H, m) ), 1.69 (6H, s) 1-728 δ = 8.09 (2H, d), 7.96 to 7.98 (3H, m), 7.89 (2H, s), 7.69 to 7.82 (8H, m), 7.25 to 7.57 (12H, m), 1.69 (6H, s) 1-731 δ = 8.38 (1H, d), 8.09 (2H, d), 7.73 to 7.98 (14H, m), 7.31 to 7.61 (10H, m), 1.69 (6H, s) 1-740 δ = 8.09 (2H, d), 7.96~7.98 (3H, m), 7.89 (2H, s), 7.69!7.82 (8H, m), 7.25~7.54 (16H, m), 1.69 (6H, s) 1-741 δ = 8.36 (2H, m), 8.08 to 8.09 (3H, m), 7.98 (1H, d), 7.88 to 7.89 (3H, m), 7.75 to 7.78 (4H, m), 7.25 to 7.54 (14H, m) ), 1.69 (6H, s) 1-748 δ = 8.09 (2H, d), 7.89 to 7.96 (6H, m), 7.69 to 7.82 (8H, m), 7.31 to 7.61 (14H, m), 1.69 (6H, s) 1-761 δ = 8.36 (2H, m), 7.98 to 8.08 (7H, m), 7.88 to 7.89 (3H, m), 7.78 (2H, d), 7.51 to 7.54 (3H, m), 7.31 to 7.39 (4H, m) ), 1.69 (6H, s) 1-763 δ = 8.36 (2H, m), 7.98 to 8.09 (3H, m), 7.76 to 7.89 (9H, m), 7.50 to 7.54 (5H, m) 7.31 to 7.39 (4H, m), 1.69 (6H, s) 1-768 δ = 7.96~8.09 (8H, m), 7.89 (2H, s), 7.69~7.82 (6H, m), 7.25~7.57 (13H, m), 1.69 (6H, s) 1-783 δ = no ¹ H NMR peak with 100% deuterium content 1-786 δ = no ¹ H NMR peak with 100% deuterium content 1-791 δ = no ¹ H NMR peak with 100% deuterium content 1-797 δ = 8.55 (1H, d), 8.45 (1H, d), 8.09 (2H, d), 7.89 to 7.96 (6H, m), 7.70 to 7.78 (7H, m), 7.41 to 7.56 (8H, m), 7.25 (2H, d), 1.69 (6H, s) 1-804 δ = 8.38~8.45 (2H, m), 8.03~8.09 (3H, m), 7.89~7.94 (5H, m), 7.41~7.78 (17H, m), 1.69 (6H, s) 1-810 δ = 8.45 (1H, d), 8.20 to 8.24 (2H, m), 8.09 (2H, d), 7.89 to 7.96 (6H, m), 7.75 to 7.78 (6H, m), 7.41 to 7.56 (8H, m) ), 7.25 (6H, m), 1.69 (6H, s) 1-814 δ = 8.45 (1H, d), 8.36 (2H, m), 8.03 to 8.09 (3H, m), 7.89 to 7.94 (4H, m), 7.68 to 7.78 (5H, m), 7.41 to 7.56 (8H, m) ), 7.25 (4H, s), 1.69 (6H, s) 1-819 δ = 8.55 (1H, d), 8.38 to 8.45 (2H, m), 8.09 (2H, d), 7.89 to 7.94 (5H, m), 7.70 to 7.78 (8H, m), 7.41 to 7.61 (9H, m) ), 7.25 (4H, s), 1.69 (6H, s) 1-829 δ = 8.45 (1H, d), 8.36 (2H, m), 8.20 to 8.24 (2H, m), 7.89 to 8.09 (8H, m), 7.76 to 7.82 (4H, m), 7.49 to 7.56 (6H, m) ), 7.31~7.39 (2H, m), 1.69 (6H, s) 1-832 δ = 8.45 (1H, d), 8.20 to 8.24 (2H, m), 7.89 to 8.09 (11H, m), 7.75 to 7.78 (4H, m), 7.25 to 7.56 (11H, m), 1.69 (6H, s ) 1-836 δ = 8.38~8.45 (3H, m), 8.20~8.24 (2H, m), 8.03~8.09 (3H, m), 7.89~7.94 (7H, m), 7.41~7.78 (14H, m), 1.69 (6H) , s) 1-842 δ = no ¹ H NMR peak with 100% deuterium content 1-848 δ = no ¹ H NMR peak with 100% deuterium content 1-853 δ = 8.18 (1H, s), 8.08 to 8.09 (2H, m), 7.96 to 7.98 (3H, m), 7.88 to 7.89 (2H, m), 7.68 to 7.78 (7H, m), 7.25 to 7.54 (12H , m), 1.69 (6H, s) 1-859 δ = 8.38 (1H, d), 8.18 (1H, s), 8.09 (1H, d), 7.31~7.98 (24H, m), 1.69 (6H, s) 1-864 δ = 8.18 (1H, s), 8.09 (1H, d), 7.89~7.98 (5H, m), 7.25~7.82 (24H, m), 1.69 (6H, s) 1-867 δ = 8.18 (1H, s), 8.09 (1H, d), 7.96 to 7.98 (3H, m), 7.68 to 7.89 (11H, m), 7.68 to 7.89 (11H, m), 7.25 to 7.54 (15H, m) ), 1.69 (6H, s) 1-869 δ = 8.36 (2H, m), 8.18 (1H, s), 8.08 to 8.09 (2H, m), 7.98 (1H, d), 7.88 to 7.89 (2H, m), 7.68 to 7.78 (5H, m), 7.25~7.54 (14H, m), 1.69 (6H, s) 1-877 δ = 8.38 (1H, d), 8.18 (1H, s), 8.08 to 8.09 (2H, m), 7.88 to 7.94 (4H, m), 7.25 to 7.78 (23H, m), 1.69 (6H, s) 1-891 δ = 8.18 (1H, s), 7.96 to 8.08 (7H, m), 7.68 to 7.89 (9H, m), 7.25 to 7.54 (12H, m), 1.69 (6H, s) 1-894 δ = 8.18 (1H, s), 7.96 to 8.09 (7H, m), 7.89 (1H, s), 7.68 to 7.82 (8H, m), 7.25 to 7.57 (13H, m), 1.69 (6H, s) 1-896 δ = 8.38~8.45 (2H, m), 8.18 (1H, s), 7.89~8.09 (8H, m), 7.31~7.82 (18H, m), 1.69 (6H, s) 1-899 δ = 8.55 (1H, d), 8.45 (1H, d), 8.32 (1H, d), 8.18 (1H, s), 8.08 to 8.09 (2H, m), 7.88 to 7.98 (7H, m), 7.25 to 7.78 (20H, m), 1.69 (6H, s) 1-905 δ = no ¹ H NMR peak with 100% deuterium content 1-908 δ = no ¹ H NMR peak with 100% deuterium content 1-910 δ = no ¹ H NMR peak with 100% deuterium content 1-917 δ = 8.55 (1H, d), 8.45 (1H, d), 8.18 (1H, s), 8.09 (1H, d), 7.89 to 7.96 (5H, m), 7.68 to 7.78 (8H, m), 7.41 to 7.56 (8H, m), 7.25 (2H, d), 1.69 (6H, s) 1-923 δ = 8.38~8.45 (2H, m), 8.18 (1H, s), 8.03~8.09 (2H, m), 7.89~7.94 (4H, m), 7.41~7.78 (18H, m), 1.69 (6H, s) ) 1-927 δ = 8.55 (1H, d), 8.45 (1H, d), 8.18 (1H, s), 8.09 (1H, d), 7.89 to 7.96 (5H, m), 7.68 to 7.78 (6H, m), 7.41 to 7.56 (8H, m), 7.25 (6H, m), 1.69 (6H, s) 1-935 δ = 8.45 (1H, d), 8.18 (1H, s), 8.09 to 8.12 (2H, m), 7.89 to 7.99 (7H, m), 7.41 to 7.78 (18H, m), 7.25 (2H, d), 1.69 (6H, s) 1-945 δ = 8.55 (1H, d), 8.45 (1H, d), 8.18 (1H, s), 7.89 to 8.09 (8H, m), 7.68 to 7.82 (8H, m), 7.25 to 7.56 (10H, m), 1.69 (6H, s) 1-947 δ = 8.45 (1H, d), 8.18 (1H, s), 7.89~8.12 (10H, m), 7.68~7.82 (7H, m), 7.25~7.54 (10H, m), 1.69 (6H, s) 1-962 δ = 8.36 (2H, m), 8.09 (1H, d), 7.98 (1H, d), 7.78–7.88 (8H, m), 7.65 (1H, d), 7.31–7.54 (8H, m), 7.65 ( 1H, d), 7.31~7.54 (10H, m), 1.69 (6H, s) 1-964 δ = 8.36 (2H, m), 8.09 (1H, d), 7.98 (1H, d), 7.89 (1H, s), 7.78 to 7.82 (5H, m), 7.65 to 7.69 (2H, m), 7.31 to 7.57 (11H, m), 1.69 (6H, s) 1-966 δ = 7.96~8.09 (5H, m), 7.89 (1H, s), 7.75~7.82 (8H, m), 7.65 (1H, d), 7.25~7.54 (12H, m), 1.69 (6H, s) 1-970 δ = 8.38 (1H, d), 7.89~8.09 (5H, m), 7.31~7.82 (21H, m), 1.69 (6H, s) 1-976 δ = 7.96~8.09 (5H, m), 7.89 (1H, s), 7.75~7.82 (8H, m), 7.65 (1H, d), 7.25~7.54 (16H, m), 1.69 (6H, s) 1-980 δ = 8.36 (2H, m), 8.09 (1H, d), 7.98 (1H, d), 7.89 (1H, s), 7.65 to 7.78 (7H, m), 7.25 to 7.57 (15H, m), 1.69 ( 6H, s) 1-984 δ = 8.38 (1H, d), 8.09 (1H, d), 7.94~7.98 (3H, m), 7.31~7.82 (28H, m), 1.69 (6H, s) 1-989 δ = 8.36 (2H, m), 7.98 to 8.09 (5H, m), 7.89 (1H, s), 7.76 to 7.82 (6H, m), 7.65 (1H, d), 7.31 to 7.54 (10H, m), 1.69 (6H, s) 1-994 δ = 7.96~8.09 (6H, m), 7.75~7.88 (10H, m), 7.65 (1H, d), 7.25~7.54 (12H, m), 1.69 (6H, s) 1-998 δ = 8.55 (1H, d), 8.32~8.45 (3H, m), 8.09 (1H, d), 7.89~7.98 (4H, m), 7.31~7.82 (20H, m), 1.69 (6H, s) 1-1002 δ = no ¹ H NMR peak with 100% deuterium content 1-1007 δ = no ¹ H NMR peak with 100% deuterium content 1-1012 δ = no ¹ H NMR peak with 100% deuterium content 1-1017 δ = 8.45 (1H, d), 8.09 to 8.12 (2H, m), 7.89 to 7.99 (6H, m), 7.75 to 7.79 (6H, m), 7.65 (1H, d), 7.41 to 7.56 (9H, m) ), 7.25 (2H, d), 1.69 (6H, s) 1-1020 δ = 8.38~8.45 (2H, m), 8.20~8.24 (2H, m), 8.09 (1H, d), 7.89~7.94 (4H, m), 7.41~7.79 (18H, m), 1.69 (6H, s) ) 1-1032 δ = 8.45 (1H, d), 8.20–8.24 (2H, m), 8.09 (1H, d), 7.93–7.96 (6H, m), 7.41–7.78 (19H, m), 7.25 (2H, d), 1.69 (6H, s) 1-1036 δ = 8.38 to 8.45 (2H, m), 8.20 to 8.24 (2H, m), 8.09 (1H, d), 7.89 to 7.94 (4H, m), 7.41 to 7.78 (18H, m), 7.25 (4H, s ), 1.69 (6H, s) 1-1042 δ = 8.45 (1H, d), 8.36 (2H, m), 7.89 to 8.09 (7H, m), 7.76 to 7.82 (4H, m), 7.65 to 7.68 (2H, m), 7.31 to 7.56 (9H, m) ), 1.69 (6H, s) 1-1044 δ = 8.45 (1H, d), 8.20~8.24 (2H, m), 7.89~8.09 (9H, m), 7.75~7.78 (4H, m), 7.65 (1H, d), 7.25~7.56 (12H, m) ), 1.69 (6H, s) 1-1046 δ = 8.38~8.45 (3H, m), 8.20~8.24 (2H, m), 8.03~8.09 (2H, m), 7.89~7.94 (6H, m), 7.41~7.78 (16H, m), 1.69 (6H) , s) 1-1049 δ = no ¹ H NMR peak with 100% deuterium content 1-1055 δ = no ¹ H NMR peak with 100% deuterium content 1-1057 δ = 8.36 (2H, m), 8.18 (1H, s), 8.08 (1H, d), 7.98 to 8.00 (2H, m), 7.88 (1H, d), 7.68 to 7.74 (3H, m), 7.31 to 7.57 (13H, m), 1.69 (6H, s) 1-1064 δ = 8.18 (1H, s), 7.96 to 8.00 (4H, m), 7.68 to 7.82 (7H, m), 7.25 to 7.57 (15H, m), 1.69 (6H, s) 1-1067 δ = 8.36 (2H, m), 8.18 (1H, s), 8.08 (1H, d), 7.98 to 8.00 (2H, m), 7.88 (1H, d), 7.68 to 7.75 (5H, m), 7.25 to 7.54 (15H, m), 1.69 (6H, s) 1-1072 δ = 8.18 (1H, s), 7.94 to 8.03 (6H, m), 7.25 to 7.82 (24H, m), 1.69 (6H, s) 1-1102 δ = 8.45 (1H, d), 8.36 (2H, m), 8.18 to 8.24 (3H, m), 7.93 to 8.00 (3H, m), 7.68 to 7.74 (3H, m), 7.38 to 7.57 (11H, m) ), 1.69 (6H, s) 1-1108 δ = 8.45 (1H, d), 8.18 (1H, s), 7.93 to 8.03 (6H, m), 7.68 to 7.75 (6H, m), 7.38 to 7.56 (11H, m), 7.25 (2H, d), 1.69 (6H, s) 1-1118 δ = 8.45 (1H, d), 8.18 (1H, s), 7.93 to 8.03 (6H, m), 7.41 to 7.75 (20H, m), 7.25 (2H, d), 1.69 (6H, s) 1-1149 δ = 8.36 (2H, m), 8.18 (1H, s), 8.08 to 8.09 (2H, m), 7.98 (1H, d), 7.88 to 7.89 (2H, m), 7.68 to 7.78 (5H, m), 7.31~7.54 (10H, m), 1.69 (6H, s) 1-1156 δ = 8.38 (1H, d), 8.18 (1H, s), 8.09 (1H, d), 7.89~7.98 (3H, m), 7.31~7.82 (20H, m), 1.69 (6H, s) 1-1162 δ = 8.18 (1H, s), 7.89 to 8.09 (7H, m), 7.25 to 7.82 (25H, m), 1.69 (6H, s) 1-1178 δ = 8.18 (1H, s), 7.96 to 8.09 (8H, m), 7.89 (1H, s), 7.68 to 7.82 (7H, m), 7.25 to 7.54 (12H, m), 1.69 (6H, s) 1-1180 δ = 8.18 (1H, s), 7.96 to 8.09 (7H, m), 7.89 (1H, s), 7.68 to 7.82 (7H, m), 7.25 to 7.57 (13H, m), 1.69 (6H, s) 1-1200 δ = 8.45 (1H, d), 8.18 (1H, s), 7.93 to 8.09 (7H, m), 7.68 to 7.75 (8H, m), 7.41 to 7.56 (8H, m), 7.25 (2H, d), 1.69 (6H, s) 1-1206 δ = 8.45 (1H, d), 8.36 (2H, m), 8.18 to 8.24 (3H, m), 8.09 (1H, d), 7.89 to 7.94 (3H, m), 7.68 to 7.78 (5H, m), 7.41~7.56 (8H, m), 7.25 (4H, s), 1.69 (6H, s) 1-1222 δ = 8.45 (1H, d), 8.36 (2H, m), 8.18 to 8.24 (3H, m), 7.89 to 8.09 (6H, m), 7.68 to 7.82 (5H, m), 7.49 to 7.56 (6H, m) ), 7.31~7.39 (2H, m), 1.69 (6H, s) 1-1228 δ = 8.45 (1H, d), 8.18 (1H, s), 7.89 to 8.09 (10H, m), 7.68 to 7.78 (6H, m), 7.25 to 7.56 (11H, m), 1.69 (6H, s) 1-1249 δ = 8.36 (2H, m), 8.18 (2H, s), 8.08 (1H, d), 7.98 (1H, d), 7.88 (1H, d), 7.68 to 7.75 (6H, m), 7.31 to 7.54 ( 10H, m), 1.69 (6H, s) 1-1254 δ = 8.38 (1H, d), 8.18 (2H, s), 7.31~7.98 (25H, m), 1.69 (6H, s) 1-1263 δ = 8.18 (2H, s), 8.08 (1H, d), 7.88~7.98 (5H, m), 7.25~7.75 (23H, m), 1.69 (6H, s) 1-1284 δ = 8.45 (1H, d), 8.36 (2H, m), 8.18 (2H, s), 8.03 (1H, d), 7.93 to 7.94 (2H, d), 7.68 to 7.75 (7H, m), 7.41 to 7.56 (8H, m), 1.69 (6H, s) 1-1288 δ = 8.45 (1H, d), 8.18 (2H, s), 7.93 to 8.03 (5H, m), 7.68 to 7.75 (9H, m), 7.41 to 7.56 (8H, m), 7.25 (2H, d), 1.69 (6H, s) 1-1296 δ = 8.45 (1H, d), 8.36 (2H, m), 1.18 (2H, s), 8.03 (1H, d), 7.93 to 7.94 (2H, d), 7.68 to 7.75 (7H, m), 7.41 to 7.56 (8H, m), 7.25 (4H, s), 1.69 (6H, s) 1-1313 δ = 8.18 (1H, s), 8.08 (1H, d), 7.96 to 7.98 (3H, m), 7.88 (1H, d), 7.65 to 7.79 (8H, m), 7.25 to 7.54 (13H, m), 1.69 (6H, s) 1-1316 δ = 8.18 (1H, s), 7.96 to 7.98 (3H, m), 7.65 to 7.82 (10H, m), 7.25 to 7.57 (13H, m), 1.69 (6H, s) 1-1319 δ = 8.38 (1H, d), 8.18 (1H, s), 7.31~7.98 (24H, m), 1.69 (6H, s) 1-1322 δ = 8.36 (2H, m), 8.18 (1H, s), 7.98 to 8.03 (2H, m), 7.65 to 8.03 (8H, m), 7.25 to 7.54 (14H, m), 1.69 (6H, s) 1-1328 δ = 8.18 (1H, s), 7.94 to 7.98 (4H, m), 7.25 to 7.78 (26H, m), 1.69 (6H, s) 1-1340 δ = 8.36 (2H, m), 8.18 (1H, s), 7.98 to 8.03 (3H, m), 7.65 to 7.82 (8H, m), 7.31 to 7.54 (11H, m), 1.69 (6H, s) 1-1342 δ = 8.18 (1H, s), 7.96 to 8.03 (5H, m), 7.65 to 7.88 (11H, m), 7.31 to 7.54 (12H, m), 1.69 (6H, s) 1-1349 δ = 8.55 (1H, d), 8.45 (1H, d), 8.18 (1H, s), 7.92 to 7.96 (4H, m), 7.65 to 7.79 (9H, m), 7.41 to 7.56 (9H, m), 7.25 (2H, d), 1.69 (6H, s) 1-1352 δ = 8.45 (1H, d), 8.18 (1H, s), 7.93 to 8.03 (5H, m), 7.65 to 7.79 (9H, m), 7.41 to 7.56 (9H, m), 7.25 (2H, d), 1.69 (6H, s) 1-1355 δ = 8.38 to 8.45 (2H, m), 8.18 (1H, s), 8.12 (1H, s), 7.92 to 7.99 (4H, m), 7.41 to 7.78 (19H, m), 1.69 (6H, s) 1-1367 δ = 8.45 (1H, d), 8.18 (1H, s), 8.12 (1H, s), 7.92 to 7.99 (6H, m), 7.41 to 7.78 (20H, m), 7.25 (2H, d) 1-1384 δ = no ¹ H NMR peak with 100% deuterium content 1-1386 δ = no ¹ H NMR peak with 100% deuterium content 1-1388 δ = no ¹ H NMR peak with 100% deuterium content 2-23 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13~8.19 (2H, m), 7.89~7.99 (9H, m), 7.75~7.80 (4H, m), 7.19~7.49 (8H, m) ), 7.19~7.58 (10H, m) 2-32 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.21 (2H, m), 7.89 to 7.99 (8H, m), 7.35 to 7.77 (17H, m), 7.16 to 7.20 (2H, m) ) 2-33 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.21 (4H, m), 7.89 to 7.99 (4H, m), 7.35 to 7.77 (20H, m), 7.16 to 7.25 (6H, m) ) 2-34 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.21 (3H, m), 7.89 to 7.99 (8H, m), 7.35 to 7.77 (17H, m), 7.16 to 7.25 (6H, m) ) 2-42 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.19 (2H, m), 7.89 to 7.99 (12H, m), 7.75 to 7.77 (5H, m), 7.58 (1H, d), 7.35~7.50 (8H, m), 7.16~7.20 (2H, m) 2-44 δ = 8.55 (1H, d), 8.30 (1H, d), 8.13 to 8.19 (2H, m), 7.89 to 7.99 (12H, m), 7.75 to 7.77 (5H, m), 7.58 (1H, d), 7.35~7.50 (8H, m), 7.16~7.25 (6H, m)

compound FD-Mass compound FD-Mass 1-1 m/z= 591.71 (C42H29N3O=591.23) 1-4 m/z= 591.71 (C42H29N3O=591.23) 1-5 m/z= 667.81 (C48H33N3O=667.26) 1-8 m/z= 667.81 (C48H33N3O=667.26) 1-9 m/z= 667.81 (C48H33N3O=667.26) 1-14 m/z = 743.91 (C54H37N3O=743.29) 1-18 m/z = 743.91 (C54H37N3O=743.29) 1-21 m/z= 667.81 (C48H33N3O=667.26) 1-27 m/z = 743.91 (C54H37N3O=743.29) 1-30 m/z = 743.91 (C54H37N3O=743.29) 1-41 m/z= 681.80 (C48H31N3O2=681.24) 1-42 m/z= 681.80 (C48H31N3O2=681.24) 1-47 m/z= 757.89 (C54H35N3O2=757.27) 1-49 m/z= 773.95 (C54H35N3OS=773.25) 1-61 m/z= 620.89 (C42D29N3O=620.41) 1-64 m/z= 620.89 (C42D29N3O=620.41) 1-69 m/z= 701.01 (C48D33N3O=700.47) 1-72 m/z= 701.01 (C48D33N3O=700.47) 1-73 m/z = 607.78 (C42H29N3S=607.21) 1-78 m/z= 683.87 (C48H33N3S=683.24) 1-80 m/z= 683.87 (C48H33N3S=683.24) 1-81 m/z= 683.87 (C48H33N3S=683.24) 1-86 m/z = 759.97 (C54H37N3S=759.27) 1-90 m/z = 759.97 (C54H37N3S=759.27) 1-94 m/z= 683.87 (C48H33N3S=683.24) 1-100 m/z = 759.97 (C54H37N3S=759.27) 1-113 m/z= 697.86 (C48H31N3OS=697.22) 1-118 m/z= 773.95 (C54H35N3OS=773.25) 1-124 m/z= 790.02 (C54H35N3S2=789.23) 1-133 m/z= 636.95 (C42D29N3S=636.39) 1-136 m/z= 636.95 (C42D29N3S=636.39) 1-140 m/z= 717.07 (C48D33N3S=716.45) 1-144 m/z= 717.07 (C48D33N3S=716.45) 1-145 m/z= 591.71 (C42H29N3O=591.23) 1-146 m/z= 591.71 (C42H29N3O=591.23) 1-148 m/z= 591.71 (C42H29N3O=591.23) 1-150 m/z= 667.81 (C48H33N3O=667.26) 1-154 m/z= 667.81 (C48H33N3O=667.26) 1-160 m/z = 743.91 (C54H37N3O=743.29) 1-161 m/z = 743.91 (C54H37N3O=743.29) 1-166 m/z = 743.91 (C54H37N3O=743.29) 1-171 m/z = 743.91 (C54H37N3O=743.29) 1-176 m/z = 743.91 (C54H37N3O=743.29) 1-189 m/z= 757.89 (C54H35N3O2=757.27) 1-190 m/z= 757.89 (C54H35N3O2=757.27) 1-192 m/z= 757.89 (C54H35N3O2=757.27) 1-193 m/z= 773.95 (C54H35N3OS=773.25) 1-198 m/z= 850.05 (C60H39N3OS=849.28) 1-205 m/z= 620.89 (C42D29N3O=620.41) 1-212 m/z= 701.01 (C48D33N3O=700.47) 1-215 m/z= 701.01 (C48D33N3O=700.47) 1-216 m/z= 701.01 (C48D33N3O=700.47) 1-217 m/z = 607.78 (C42H29N3S=607.21) 1-221 m/z= 683.87 (C48H33N3S=683.24) 1-222 m/z= 683.87 (C48H33N3S=683.24) 1-232 m/z = 759.97 (C54H37N3S=759.27) 1-236 m/z = 759.97 (C54H37N3S=759.27) 1-239 m/z= 683.87 (C48H33N3S=683.24) 1-244 m/z = 759.97 (C54H37N3S=759.27) 1-257 m/z= 697.86 (C48H31N3OS=697.22) 1-262 m/z= 773.95 (C54H35N3OS=773.25) 1-268 m/z= 790.02 (C54H35N3S2=789.23) 1-277 m/z= 636.95 (C42D29N3S=636.39) 1-278 m/z= 636.95 (C42D29N3S=636.39) 1-280 m/z= 636.95 (C42D29N3S=636.39) 1-283 m/z= 717.07 (C48D33N3S=716.45) 1-287 m/z= 717.07 (C48D33N3S=716.45) 1-289 m/z= 591.71 (C42H29N3O=591.23) 1-294 m/z= 667.81 (C48H33N3O=667.26) 1-296 m/z= 667.81 (C48H33N3O=667.26) 1-300 m/z= 667.81 (C48H33N3O=667.26) 1-304 m/z = 743.91 (C54H37N3O=743.29) 1-311 m/z= 667.81 (C48H33N3O=667.26) 1-313 m/z = 743.91 (C54H37N3O=743.29) 1-329 m/z= 681.80 (C48H31N3O2=681.24) 1-334 m/z= 757.89 (C54H35N3O2=757.27) 1-340 m/z= 773.95 (C54H35N3OS=773.25) 1-349 m/z= 620.89 (C42D29N3O=620.41) 1-356 m/z= 701.01 (C48D33N3O=700.47) 1-360 m/z= 701.01 (C48D33N3O=700.47) 1-361 m/z = 607.78 (C42H29N3S=607.21) 1-365 m/z= 683.87 (C48H33N3S=683.24) 1-368 m/z= 683.87 (C48H33N3S=683.24) 1-374 m/z = 759.97 (C54H37N3S=759.27) 1-382 m/z= 683.87 (C48H33N3S=683.24) 1-384 m/z= 683.87 (C48H33N3S=683.24) 1-388 m/z = 759.97 (C54H37N3S=759.27) 1-401 m/z= 697.86 (C48H31N3OS=697.22) 1-407 m/z= 773.95 (C54H35N3OS=773.25) 1-411 m/z= 773.95 (C54H35N3OS=773.25) 1-422 m/z= 636.95 (C42D29N3S=636.39) 1-426 m/z= 717.07 (C48D33N3S=716.45) 1-432 m/z= 717.07 (C48D33N3S=716.45) 1-433 m/z= 591.71 (C42H29N3O=591.23) 1-437 m/z= 667.81 (C48H33N3O=667.26) 1-448 m/z = 743.91 (C54H37N3O=743.29) 1-456 m/z= 667.81 (C48H33N3O=667.26) 1-474 m/z= 681.80 (C48H31N3O2=681.24) 1-478 m/z= 757.89 (C54H35N3O2=757.27) 1-480 m/z= 757.89 (C54H35N3O2=757.27) 1-493 m/z= 620.89 (C42D29N3O=620.41) 1-495 m/z= 620.89 (C42D29N3O=620.41) 1-498 m/z= 701.01 (C48D33N3O=700.47) 1-510 m/z= 683.87 (C48H33N3S=683.24) 1-512 m/z= 683.87 (C48H33N3S=683.24) 1-520 m/z = 759.97 (C54H37N3S=759.27) 1-532 m/z = 759.97 (C54H37N3S=759.27) 1-534 m/z = 759.97 (C54H37N3S=759.27) 1-546 m/z= 697.86 (C48H31N3OS=697.22) 1-551 m/z= 773.95 (C54H35N3OS=773.25) 1-555 m/z= 790.02 (C54H35N3S2=789.23) 1-560 m/z= 866.11 (C60H39N3S2=865.26) 1-568 m/z= 636.95 (C42D29N3S=636.39) 1-570 m/z= 717.07 (C48D33N3S=716.45) 1-574 m/z= 717.07 (C46D33N3S=716.45) 1-577 m/z= 591.71 (C42H29N3O=591.23) 1-580 m/z= 591.71 (C42H29N3O=591.23) 1-583 m/z= 667.81 (C48H33N3O=667.26) 1-598 m/z= 667.81 (C48H33N3O=667.26) 1-600 m/z= 667.81 (C48H33N3O=667.26) 1-617 m/z= 681.80 (C48H31B3O2=681.24) 1-620 m/z= 681.80 (C48H31N3O2=681.24) 1-623 m/z= 757.89 (C54H35N3O2=757.27) 1-628 m/z= 757.89 (C54H35N3O2=757.27) 1-637 m/z= 620.89 (C42D29N3O=620.42) 1-642 m/z= 701.01 (C48D33N3O=700.47) 1-647 m/z= 701.01 (C48D33N3O=700.47) 1-653 m/z= 683.87 (C48H33N3S=683.24) 1-655 m/z= 683.87 (C48H33N3S=683.24) 1-659 m/z= 683.87 (C48H33N3S=683.24) 1-670 m/z= 683.87 (C48H33N3S=683.24) 1-690 m/z= 697.86 (C48H31N3OS=697.22) 1-691 m/z= 697.86 (C48H31N3OS=697.22) 1-693 m/z= 773.95 (C54H35N3OS=773.25) 1-699 m/z= 773.95 (C54H35N3OS=773.25) 1-710 m/z= 636.95 (C42D29N3S=636.39) 1-713 m/z= 717.07 (C48D33N3S=716.45) 1-718 m/z= 717.07 (C48D33N3S=716.45) 1-721 m/z= 591.71 (C42H29N3O=591.23) 1-728 m/z= 667.81 (C48H33N3O=667.26) 1-731 m/z= 667.81 (C48H33N3O=667.26) 1-740 m/z = 743.91 (C54H37N3O=743.29) 1-741 m/z= 667.81 (C48H33N3O=667.26) 1-748 m/z= 667.81 (C48H33N3O=667.26) 1-761 m/z= 681.80 (C48H31N3O2=681.24) 1-763 m/z= 681.80 (C48H31N3O2=681.24) 1-768 m/z= 757.89 (C54H35N3O2=757.27) 1-783 m/z= 620.89 (C42D29N3O=620.41) 1-786 m/z= 701.01 (C48D33N3O=700.47) 1-791 m/z= 701.01 (C48D33N3O=700.47) 1-797 m/z = 683.87 (C48H33N3S=683.87) 1-804 m/z= 683.87 (C48H33N3S=683.24) 1-810 m/z = 759.87 (C54H37N3S=759.27) 1-814 m/z= 683.87 (C48H33N3S=683.24) 1-819 m/z = 759.97 (C54H37N3S=759.27) 1-829 m/z= 697.86 (C48H31N3OS=697.22) 1-832 m/z= 773.95 (C54H35N3OS=773.25) 1-836 m/z= 790.02 (C54H35N3S2=789.23) 1-842 m/z= 717.07 (C48D33N3S=716.45) 1-848 m/z= 717.07 (C48D33N3S=716.45) 1-853 m/z= 667.81 (C48H33N3O=667.26) 1-859 m/z= 667.81 (C48H33N3O=667.26) 1-864 m/z = 743.91 (C54H37N3O=743.29) 1-867 m/z = 743.91 (C54H37N3O=743.29) 1-869 m/z = 743.91 (C54H37N3O=743.29) 1-877 m/z = 743.91 (C54H37N3O=743.29) 1-891 m/z= 757.89 (C54H35N3O2=757.27) 1-894 m/z= 757.89 (C54H35N3O2=757.27) 1-896 m/z= 773.95 (C54H35N3OS=773.25) 1-899 m/z= 850.05 (C60H39N3OS=849.28) 1-905 m/z= 701.01 (C48D33N3O=700.47) 1-908 m/z= 701.01 (C48D33N3O=700.47) 1-910 m/z= 701.01 (C48D33N3O=700.47) 1-917 m/z= 683.87 (C48H33N3S=683.24) 1-923 m/z= 683.87 (C48H33N3S=683.24) 1-927 m/z = 759.97 (C54H37N3S=759.27) 1-935 m/z = 759.97 (C54H37N3S=759.27) 1-945 m/z= 773.95 (C54H35N3OS=773.25) 1-947 m/z= 773.95 (C54H35N3OS=773.25) 1-962 m/z= 591.71 (C42H29N3O=591.23) 1-964 m/z= 591.71 (C42H29N3O=591.23) 1-966 m/z= 667.81 (C48H33N3O=667.26) 1-970 m/z= 667.81 (C48H33N3O=667.26) 1-976 m/z = 743.91 (C54H37N3O=743.29) 1-980 m/z= 667.81 (C48H33N3O=667.26) 1-984 m/z = 743.91 (C54H37N3O=743.29) 1-989 m/z= 681.80 (C48H31N3O2=681.24) 1-994 m/z= 757.89 (C54H35N3O2=757.27) 1-998 m/z= 773.95 (C54H35N3OS=773.25) 1-1002 m/z= 620.89 (C42D29N3O=620.41) 1-1007 m/z= 701.01 (C48D33N3O=700.47) 1-1012 m/z= 701.01 (C48D33N3O=700.47) 1-1017 m/z= 683.87 (C48H33N3S=683.24) 1-1020 m/z= 683.87 (C48H33N3S=683.24) 1-1032 m/z = 759.97 (C54H37N3S=759.27) 1-1036 m/z = 759.97 (C54H37N3S=759.27) 1-1042 m/z= 697.86 (C48H31N3OS=697.22) 1-1044 m/z= 773.95 (C54H35N3OS=773.25) 1-1046 m/z= 790.02 (C54H35N3S2=789.23) 1-1049 m/z= 717.07 (C48D33N3S=716.45) 1-1055 m/z= 717.07 (C48D33N3S=716.45) 1-1057 m/z= 591.71 (C42H29N3O=591.23) 1-1064 m/z= 667.81 (C48H33N3O=667.26) 1-1067 m/z= 667.81 (C48H33N3O=667.26) 1-1072 m/z = 743.91 (C54H37N3O=743.29) 1-1102 m/z = 607.78 (C42H29N3S=607.21) 1-1108 m/z= 683.87 (C48H33N2S=683.24) 1-1118 m/z = 759.97 (C54H37N3S=759.27) 1-1149 m/z= 591.71 (C42H29N3O=591.23) 1-1156 m/z= 667.81 (C48H33N3O=667.26) 1-1162 m/z= 667.81 (C48H33N3O=667.26) 1-1178 m/z= 757.89 (C54H35N3O2=757.27) 1-1180 m/z= 757.89 (C54H35N3O2=757.27) 1-1200 m/z= 683.87 (C48H33N3S=683.24) 1-1206 m/z= 683.87 (C48H33N3S=683.24) 1-1222 m/z= 697.86 (C48H31N3OS=697.22) 1-1228 m/z= 773.95 (C54H35N3OS=773.25) 1-1249 m/z= 591.71 (C42H29N3O=591.23) 1-1254 m/z= 667.81 (C48H33N3O=667.26) 1-1263 m/z = 743.91 (C54H37N3O=743.29) 1-1284 m/z = 607.78 (C42H29N3S=607.21) 1-1288 m/z= 683.87 (C48H33N3S=683.24) 1-1296 m/z= 683.87 (C48H33N3S=683.24) 1-1313 m/z= 667.81 (C48H33N3O=667.26) 1-1316 m/z= 667.81 (C48H33N3O=667.26) 1-1319 m/z= 667.81 (C48H33N3O=667.26) 1-1322 m/z= 667.81 (C48H33N3O=667.26) 1-1328 m/z = 743.91 (C54H37N3O=743.29) 1-1340 m/z= 681.80 (C48H31N3O2=681.24) 1-1342 m/z= 757.89 (C54H35N3O2=757.27) 1-1349 m/z= 683.87 (C48H33N3S=683.24) 1-1352 m/z= 683.87 (C48H33N3S=683.24) 1-1367 m/z = 759.97 (C54H37N3S=759.27) 1-1384 m/z= 717.07 (C48D33N3S=716.45) 1-1386 m/z= 717.07 (C48D33N3S=716.45) 1-1388 m/z= 717.07 (C48D33N3S=716.45) 2-23 m/z= 712.90 (C54H36N2=712.29) 2-32 m/z= 636.80 (C48H32N2=636.26) 2-33 m/z= 712.90 (C54H36N2=712.29) 2-34 m/z= 712.90 (C54H36N2=712.29) 2-42 m/z= 636.80 (C48H32N2=636.26) 2-44 m/z= 712.90 (C54H36N2=712.29)

<Experimental Example 1>

1) Fabrication 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, it was ultrasonically washed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UVO 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 then 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 emission layer was deposited at 400 Å by doping Ir(ppy) ₃ to the host at 7% of the deposition thickness of the emission layer using the compounds listed in Table 6 as a host and Ir(ppy) ₃ (tris(2-phenylpyridine)iridium) as a green phosphorescent dopant. did Thereafter, 60 Å of bathocuproine (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) was deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode was deposited on the electron injection layer to a thickness of 1200 Å to form a negative electrode Comparative Example Organic light emitting devices of 1 to 6 and Examples 1 to 237 were prepared.

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) Driving Voltage and Luminous Efficiency of Organic Light-Emitting Devices

The electroluminescence (EL) characteristics of the organic light emitting devices of Comparative Examples 1 to 6 and Examples 1 to 237 prepared as described above were measured with McSyers M7000, and life equipment manufactured by McScience with the measurement results. When the standard luminance is 6,000 cd/m ² through the measuring equipment (M6000), T ₉₀ (unit: h, time), which is the time to reach 90% of the initial luminance, was measured.

The results were shown in Table 6 below.

compound drive voltage
(V) efficiency
(cd/A) color coordinates life span
(T ₉₀ ) Comparative Example 1 A 6.21 45.3 Green 65 Comparative Example 2 B 6.50 40.5 Green 51 Comparative Example 3 C 6.48 41.2 Green 53 Comparative Example 4 D 6.38 43.7 Green 63 Comparative Example 5 E 6.42 42.9 Green 59 Comparative Example 6 F 6.33 44.3 Green 60 Example 1 1-1 3.97 65.9 Green 105 Example 2 1-4 4.29 66.3 Green 110 Example 3 1-5 4.58 65.1 Green 203 Example 4 1-8 4.69 66.9 Green 240 Example 5 1-9 4.57 66.5 Green 241 Example 6 1-14 4.63 68.7 Green 244 Example 7 1-18 4.59 69.4 Green 119 Example 8 1-21 4.67 70.9 Green 123 Example 9 1-27 4.56 71.6 Green 125 Example 10 1-30 4.38 70.2 Green 121 Example 11 1-41 3.55 80.2 Green 132 Example 12 1-42 3.63 77.6 Green 144 Example 13 1-47 3.50 78.2 Green 140 Example 14 1-49 3.61 79.6 Green 156 Example 15 1-61 3.55 66.7 Green 155 Example 16 1-64 3.64 63.7 Green 157 Example 17 1-69 3.57 66.2 Green 200 Example 18 1-72 3.49 68.4 Green 205 Example 19 1-73 4.55 69.1 Green 209 Example 20 1-78 4.38 71.2 Green 108 Example 21 1-80 4.36 70.3 Green 113 Example 22 1-81 4.25 66.7 Green 120 Example 23 1-86 4.93 65.9 Green 119 Example 24 1-90 4.87 67.0 Green 132 Example 25 1-94 4.56 66.2 Green 142 Example 26 1-100 4.32 65.8 Green 155 Example 27 1-113 3.49 78.6 Green 169 Example 28 1-118 3.59 77.2 Green 171 Example 29 1-124 3.62 79.8 Green 173 Example 30 1-133 4.05 68.1 Green 185 Example 31 1-136 3.89 67.8 Green 180 Example 32 1-140 4.32 68.8 Green 128 Example 33 1-144 4.59 69.5 Green 193 Example 34 1-145 4.68 67.2 Green 216 Example 35 1-146 4.22 66.5 Green 228 Example 36 1-148 4.13 75.2 Green 236 Example 37 1-150 4.08 73.6 Green 244 Example 38 1-154 4.53 74.4 Green 250 Example 39 1-160 4.67 73.9 Green 176 Example 40 1-161 4.69 70.5 Green 180 Example 41 1-166 4.33 76.2 Green 183 Example 42 1-171 4.38 75.3 Green 195 Example 43 1-176 4.21 74.8 Green 243 Example 44 1-189 3.76 74.9 Green 247 Example 45 1-190 3.66 76.8 Green 216 Example 46 1-192 3.73 77.9 Green 209 Example 47 1-193 3.61 78.3 Green 213 Example 48 1-198 3.68 80.2 Green 233 Example 49 1-205 4.38 73.5 Green 211 Example 50 1-212 4.12 70.9 Green 247 Example 51 1-215 3.78 72.6 Green 243 Example 52 1-216 3.90 71.4 Green 115 Example 53 1-217 3.87 70.7 Green 128 Example 54 1-221 4.02 69.5 Green 132 Example 55 1-232 3.99 66.1 Green 142 Example 56 1-236 4.67 68.5 Green 150 Example 57 1-239 4.88 69.7 Green 169 Example 58 1-244 5.01 70.3 Green 173 Example 59 1-257 3.68 77.2 Green 177 Example 60 1-262 3.83 78.8 Green 159 Example 61 1-268 3.77 79.3 Green 162 Example 62 1-277 4.53 65.7 Green 187 Example 63 1-278 4.23 69.5 Green 193 Example 64 1-280 4.77 67.8 Green 207 Example 65 1-283 4.89 66.2 Green 200 Example 66 1-287 5.02 65.9 Green 189 Example 67 1-289 4.86 70.5 Green 163 Example 68 1-294 4.60 77.2 Green 209 Example 69 1-296 4.68 79.3 Green 213 Example 70 1-300 4.71 78.9 Green 222 Example 71 1-304 4.76 76.3 Green 253 Example 72 1-311 4.56 80.1 Green 300 Example 73 1-313 4.26 77.9 Green 297 Example 74 1-329 3.51 85.2 Green 283 Example 75 1-334 3.62 84.9 Green 198 Example 76 1-340 3.55 85.3 Green 205 Example 77 1-349 4.87 78.6 Green 283 Example 78 1-356 4.77 74.7 Green 255 Example 79 1-360 4.49 70.5 Green 249 Example 80 1-361 4.98 69.3 Green 269 Example 81 1-365 5.01 77.2 Green 298 Example 82 1-368 4.59 74.6 Green 277 Example 83 1-374 4.77 73.6 Green 268 Example 84 1-382 4.83 70.6 Green 265 Example 85 1-384 4.76 73.2 Green 261 Example 86 1-388 4.68 74.2 Green 255 Example 87 1-401 3.63 84.7 Green 237 Example 88 1-407 3.67 83.3 Green 251 Example 89 1-411 3.59 85.0 Green 255 Example 90 1-422 4.78 69.6 Green 263 Example 91 1-426 4.69 65.3 Green 271 Example 92 1-432 4.52 67.7 Green 283 Example 93 1-433 4.69 68.2 Green 279 Example 94 1-437 4.77 69.6 Green 281 Example 95 1-448 4.86 81.3 Green 264 Example 96 1-456 4.66 80.5 Green 250 Example 97 1-474 3.51 84.2 Green 255 Example 98 1-478 3.56 83.6 Green 263 Example 99 1-480 3.63 84.9 Green 271 Example 100 1-493 4.87 69.3 Green 283 Example 101 1-495 4.89 68.2 Green 269 Example 102 1-498 4.58 69.3 Green 251 Example 103 1-510 4.53 67.5 Green 263 Example 104 1-512 4.67 68.2 Green 283 Example 105 1-520 4.44 66.7 Green 285 Example 106 1-532 4.56 72.9 Green 291

Example 107 1-534 4.69 70.4 Green 297 Example 108 1-546 3.63 84.7 Green 169 Example 109 1-551 3.60 83.6 Green 177 Example 110 1-555 3.51 84.7 Green 209 Example 111 1-560 3.55 83.2 Green 213 Example 112 1-568 4.88 67.3 Green 228 Example 113 1-570 4.87 66.9 Green 197 Example 114 1-574 5.02 65.8 Green 206 Example 115 1-577 4.40 82.6 Green 235 Example 116 1-580 4.47 81.6 Green 244 Example 117 1-583 4.39 80.9 Green 302 Example 118 1-597 4.26 82.6 Green 313 Example 119 1-600 4.11 88.5 Green 320 Example 120 1-617 3.08 95.2 Green 349 Example 121 1-620 3.11 91.3 Green 350 Example 122 1-623 3.20 93.7 Green 216 Example 123 1-628 3.12 90.4 Green 225 Example 124 1-637 4.36 82.3 Green 263 Example 125 1-642 4.28 80.6 Green 274 Example 126 1-644 4.37 83.9 Green 288 Example 127 1-647 4.43 84.2 Green 291 Example 128 1-653 4.50 86.5 Green 293 Example 129 1-655 4.69 87.2 Green 287 Example 130 1-659 4.33 89.3 Green 246 Example 131 1-670 4.28 88.6 Green 240 Example 132 1-690 3.09 94.7 Green 251 Example 133 1-692 3.19 94.4 Green 249 Example 134 1-693 3.25 94.7 Green 263 Example 135 1-699 3.12 95.2 Green 264 Example 136 1-710 4.36 84.7 Green 271 Example 137 1-713 4.37 85.2 Green 280 Example 138 1-718 4.29 84.9 Green 261 Example 139 1-721 4.43 83.5 Green 255 Example 140 1-728 4.46 80.1 Green 206 Example 141 1-731 4.51 84.6 Green 216 Example 142 1-740 4.30 85.6 Green 223 Example 143 1-741 4.29 83.7 Green 243 Example 144 1-748 4.35 82.6 Green 253 Example 145 1-761 3.20 93.7 Green 261 Example 146 1-763 3.17 94.3 Green 259 Example 147 1-768 3.05 93.1 Green 263 Example 148 1-783 4.39 81.3 Green 271 Example 149 1-786 4.23 80.9 Green 216 Example 150 1-791 4.52 83.4 Green 228 Example 151 1-797 4.36 87.2 Green 236 Example 152 1-804 4.26 88.6 Green 246 Example 153 1-810 4.44 85.9 Green 259 Example 154 1-814 4.39 82.6 Green 263 Example 155 1-819 4.23 81.6 Green 261 Example 156 1-829 3.26 94.2 Green 257 Example 157 1-832 3.10 93.6 Green 263 Example 158 1-836 3.06 91.7 Green 249 Example 159 1-842 4.44 83.5 Green 230 Example 160 1-848 4.23 80.7 Green 231 Example 161 1-853 4.30 87.2 Green 259 Example 162 1-859 4.48 90.5 Green 249 Example 163 1-864 4.26 83.2 Green 251 Example 164 1-867 4.31 83.5 Green 266 Example 165 1-869 4.37 84.4 Green 268 Example 166 1-877 4.45 80.3 Green 333 Example 167 1-891 3.05 96.2 Green 329 Example 168 1-894 3.09 95.4 Green 312 Example 169 1-896 3.26 94.7 Green 344 Example 170 1-899 3.12 95.9 Green 346 Example 171 1-905 4.33 92.2 Green 357 Example 172 1-908 4.38 91.6 Green 326 Example 173 1-910 4.29 92.4 Green 343 Example 174 1-917 4.41 88.7 Green 337 Example 175 1-923 4.47 89.2 Green 341 Example 176 1-927 4.36 86.3 Green 348 Example 177 1-935 4.25 87.7 Green 322 Example 178 1-945 3.11 94.7 Green 246 Example 179 1-947 3.26 93.6 Green 237 Example 180 1-962 4.31 91.5 Green 249 Example 181 1-964 4.23 90.3 Green 253 Example 182 1-966 4.14 89.3 Green 261 Example 183 1-970 4.09 85.2 Green 243 Example 184 1-976 4.13 84.6 Green 234 Example 185 1-980 3.79 88.3 Green 225 Example 186 1-984 3.68 81.7 Green 219 Example 187 1-989 3.25 95.5 Green 311 Example 188 1-994 3.22 96.0 Green 238 Example 189 1-998 3.34 94.9 Green 223 Example 190 1-1002 4.30 87.3 Green 219 Example 191 1-1007 4.29 86.5 Green 206 Example 192 1-1012 4.33 84.7 Green 273 Example 193 1-1017 4.21 87.6 Green 332 Example 194 1-1020 4.50 88.3 Green 349 Example 195 1-1032 4.33 82.9 Green 350 Example 196 1-1036 4.26 81.7 Green 325 Example 197 1-1042 3.09 94.7 Green 313 Example 198 1-1044 3.12 95.6 Green 302 Example 199 1-1046 3.28 95.9 Green 255 Example 200 1-1049 4.36 85.3 Green 246 Example 201 1-1055 4.42 83.7 Green 231 Example 202 1-1057 5.91 54.4 Green 89 Example 203 1-1064 5.83 53.7 Green 98 Example 204 1-1067 5.76 54.2 Green 93 Example 205 1-1072 5.79 56.8 Green 91 Example 206 1-1102 5.68 55.1 Green 83 Example 207 1-1108 5.99 59.3 Green 76 Example 208 1-1118 5.91 57.6 Green 88 Example 209 1-1149 5.89 56.2 Green 91 Example 210 1-1156 5.78 53.8 Green 103 Example 211 1-1162 6.01 50.7 Green 99 Example 212 1-1178 5.51 65.2 Green 93 Example 213 1-1180 5.62 64.7 Green 87 Example 214 1-1200 5.73 53.9 Green 86 Example 215 1-1206 5.89 51.7 Green 91 Example 216 1-1222 5.63 64.2 Green 98 Example 217 1-1228 5.61 65.5 Green 103 Example 218 1-1249 5.48 67.2 Green 85 Example 219 1-1254 5.33 69.3 Green 100 Example 220 1-1263 5.21 68.5 Green 105 Example 221 1-1284 5.32 67.2 Green 93 Example 222 1-1288 5.49 69.3 Green 97 Example 223 1-1296 5.60 65.1 Green 100 Example 224 1-1313 5.53 66.2 Green 89 Example 225 1-1316 5.49 63.8 Green 88 Example 226 1-1319 5.34 61.2 Green 99 Example 227 1-1322 5.28 65.2 Green 91 Example 228 1-1328 5.16 69.7 Green 101 Example 229 1-1340 5.21 70.2 Green 93 Example 230 1-1342 5.13 67.9 Green 90 Example 231 1-1349 5.42 61.5 Green 89 Example 232 1-1352 5.37 60.8 Green 88 Example 233 1-1355 5.29 63.7 Green 105 Example 234 1-1367 5.44 61.8 Green 102 Example 235 1-1384 5.61 59.3 Green 96 Example 236 1-1386 5.53 55.7 Green 97 Example 237 1-1388 5.49 60.3 Green 89

Compounds A to F used in Comparative Examples 1 to 6 of Table 6 were as follows.

As can be seen from the results of Table 6, the organic light emitting device using the compound represented by Formula 1 of the present invention as a host of the green organic light emitting device has a lower driving voltage, luminous efficiency and lifespan compared to Comparative Examples 1 to 6. Significant improvement was found.

This is because the heterocyclic compound represented by Formula 1 has a structure using fluorene as a core, and the distance between molecules is closer when stacked on a substrate due to the planar structural characteristics of fluorene. It is thought to be

That is, since the intermolecular distance is closer when stacked, intermolecular electron transport becomes smoother, which may cause an effect of lowering the driving voltage.

In addition, due to the weaker hole transport ability of fluorene than that of carbazole, the heterocyclic compound represented by Chemical Formula 1 has relatively low HOMO and LUMO values.

Therefore, hole traps and electron blocking can be reduced when holes and electrons pass from the auxiliary layer to the emission material layer (EML), respectively, and the charge balance of the emission layer (EML) Since it is easy to match the performance of the organic light emitting device using the compound represented by Formula 1 of the invention as a host of the green organic light emitting device is more excellent.

In addition, when the compound represented by Chemical Formula 1 contains deuterium, it was confirmed that the device using the compound containing deuterium was more excellent than when it did not contain deuterium. This is because, when deuterium is included, the photochemical characteristics are similar, but when deposited in a thin film, the deuterium-containing material tends to be packed with a narrower intermolecular distance.

More specifically, the higher the content of deuterium, that is, the higher the substitution rate of deuterium, the better the performance of the device using the deuterium.

In addition, when only a specific substituent in Formula 1 is partially substituted with deuterium, the substituent corresponding to Ar1 in Formula 1 is substituted with deuterium, rather than a dibenzofuran group, dibenzothiophene group or fluorene in Formula 1 It was confirmed that the substitution of deuterium in the portion corresponding to can further improve the performance of the device using the heterocyclic compound represented by Formula 1.

<Experimental Example 2>

1) Fabrication 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, it was ultrasonically washed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UVO 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 then 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. Specifically, the light emitting layer was deposited to a thickness of 400 Å in one park after pre-mixing two types of compounds as shown in Table 7 below as a host, and Ir(ppy) ₃ as a green phosphorescent dopant was used at 7 of the deposition thickness of the light emitting layer. % doped and deposited.

Thereafter, BCP was deposited to a thickness of 60 Å as a hole blocking layer, and Alq ₃ was deposited to a thickness of 200 Å as an electron transport layer thereon.

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 negative electrode. Comparison Organic light-emitting devices of Examples 7 to 24 and Examples 238 to 947 were prepared.

In Table 7 below, the ratio means the weight ratio of the two compounds used as hosts. For example, Example 942 in Table 7 below means that compounds 1-1386 and 2-32 were used as hosts in a weight ratio of 1:1.

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) Driving voltage and luminous efficiency of organic light emitting device

Electroluminescence (EL) characteristics of the organic light emitting devices of Comparative Examples 7 to 24 and Examples 238 to 947 prepared as described above were measured with McSyers M7000, and life equipment manufactured by McScience with the measurement results. When the standard luminance is 6,000 cd/m ² through the measuring equipment (M6000), T ₉₀ (unit: h, time), which is the time to reach 90% of the initial luminance, was measured.

The results were shown in Table 7 below.

light emitting layer
compound ratio drive voltage
(V) efficiency
(cd/A) color coordinates life span
(T ₉₀ ) Comparative Example 7 [A]: 2-56 1:1 5.43 65.0 Green 93 Comparative Example 8 1:2 5.38 64.7 Green 98 Comparative Example 9 1:3 5.31 64.1 Green 100 Comparative Example 10 [B]: 2-60 1:1 5.69 64.3 Green 103 Comparative Example 11 1:2 5.62 64.2 Green 111 Comparative Example 12 1:3 5.59 63.7 Green 115 Comparative Example 13 [C]: 2-50 1:1 5.73 61.7 Green 98 Comparative Example 14 1:2 5.71 61.0 Green 103 Comparative Example 15 1:3 5.68 60.7 Green 111 Comparative Example 16 [D]: 2-53 1:1 5.77 63.7 Green 105 Comparative Example 17 1:2 5.74 63.2 Green 113 Comparative Example 18 1:3 5.71 61.5 Green 115 Comparative Example 19 [E]: 2-68 1:1 5.68 66.5 Green 109 Comparative Example 20 1:2 5.62 65.4 Green 113 Comparative Example 21 1:3 5.57 64.3 Green 118 Comparative Example 22 [F]: 2-56 1:1 5.88 65.7 Green 99 Comparative Example 23 1:2 5.84 65.5 Green 103 Comparative Example 24 1:3 5.76 64.7 Green 112 Example 238 1-1:2-33 1:1 3.38 88.3 Green 355 Example 239 1:2 3.32 87.2 Green 362 Example 240 1:3 3.26 86.2 Green 365 Example 241 1-4:2-34 1:1 3.44 86.9 Green 363 Example 242 1:2 3.42 86.6 Green 366 Example 243 1:3 3.39 85.3 Green 371 Example 244 1-5:2-44 1:1 3.36 87.9 Green 385 Example 245 1:2 3.32 87.3 Green 389 Example 246 1:3 3.26 86.2 Green 392 Example 247 1-8:2-23 1:1 3.37 89.5 Green 300 Example 248 1:2 3.31 88.3 Green 313 Example 249 1:3 3.29 87.2 Green 323 Example 250 1-9:2-33 1:1 3.27 90.5 Green 289 Example 251 1:2 3.21 89.2 Green 293 Example 252 1:3 3.20 88.5 Green 299 Example 253 1-14:2-44 1:1 3.29 92.6 Green 287 Example 254 1:2 3.25 91.3 Green 293 Example 255 1:3 3.21 90.2 Green 300 Example 256 1-18:2-32 1:1 3.29 89.3 Green 279 Example 257 1:2 3.26 88.2 Green 283 Example 258 1:3 3.20 87.3 Green 288 Example 259 1-21:2-33 1:1 3.33 86.9 Green 279 Example 260 1:2 3.31 86.2 Green 283 Example 261 1:3 3.29 85.9 Green 285 Example 262 1-27:2-34 1:1 3.43 89.3 Green 279 Example 263 1:2 3.42 88.4 Green 283 Example 264 1:3 3.30 87.6 Green 285 Example 265 1-30:2-34 1:1 3.38 88.3 Green 284 Example 266 1:2 3.35 87.2 Green 289 Example 267 1:3 3.31 86.7 Green 293 Example 268 1-41:2-32 1:1 2.63 93.7 Green 312 Example 269 1:2 2.61 93.1 Green 323 Example 270 1:3 2.59 92.5 Green 334 Example 271 1-42:2-33 1:1 2.62 94.7 Green 329 Example 272 1:2 2.60 94.2 Green 338 Example 273 1:3 2.58 93.8 Green 342 Example 274 1-47:2-32 1:1 2.66 95.0 Green 344 Example 275 1:2 2.63 94.7 Green 352 Example 276 1:3 2.59 94.3 Green 361 Example 277 1-49:2-42 1:1 2.59 94.5 Green 359 Example 278 1:2 2.55 94.0 Green 362 Example 279 1:3 2.51 93.7 Green 366 Example 280 1-61:2-33 1:1 3.39 89.3 Green 382 Example 281 1:2 3.35 88.2 Green 396 Example 281 1:3 3.31 87.9 Green 399 Example 282 1-64:2-44 1:1 3.37 88.3 Green 346 Example 283 1:2 3.35 87.0 Green 357 Example 284 1:3 3.31 86.9 Green 360 Example 285 1-72:2-34 1:1 3.29 91.5 Green 359 Example 286 1:2 3.25 90.3 Green 366 Example 287 1:3 3.21 89.2 Green 372 Example 288 1-73:2-42 1:1 3.38 89.7 Green 370 Example 289 1:2 3.35 88.3 Green 378 Example 290 1:3 3.32 87.3 Green 389 Example 291 1-78:2-44 1:1 3.44 93.2 Green 379 Example 292 1:2 3.42 92.7 Green 382 Example 293 1:3 3.39 92.3 Green 391 Example 294 1-80:2-32 1:1 3.35 89.7 Green 381 Example 295 1:2 3.31 88.3 Green 388 Example 296 1:3 3.28 87.6 Green 392 Example 297 1-81:2-33 1:1 3.38 88.7 Green 356 Example 298 1:2 3.32 87.3 Green 359 Example 299 1:3 3.27 86.2 Green 366 Example 300 1-86 :2-32 1:1 3.39 89.2 Green 348 Example 301 1:2 3.38 88.7 Green 350 Example 302 1:3 3.25 87.3 Green 359 Example 303 1-90:2-42 1:1 3.42 90.7 Green 328 Example 304 1:2 3.40 89.3 Green 339 Example 305 1:3 3.35 88.1 Green 348 Example 306 1-94:2-44 1:1 3.32 88.3 Green 355 Example 307 1:2 3.30 87.3 Green 362 Example 308 1:3 3.27 86.2 Green 369 Example 309 1-100:2-33 1:1 3.22 87.6 Green 372 Example 310 1:2 3.18 87.3 Green 377 Example 311 1:3 3.12 85.0 Green 386 Example 312 1-113:2-33 1:1 2.87 90.8 Green 383 Example 313 1:2 2.85 89.9 Green 392 Example 314 1:3 2.80 89.2 Green 397 Example 315 1-118:2-42 1:1 2.76 94.7 Green 348 Example 316 1:2 2.74 94.2 Green 352 Example 317 1:3 2.73 93.3 Green 369 Example 318 1-124:2-32 1:1 2.67 94.8 Green 366 Example 319 1:2 2.64 93.2 Green 372 Example 320 1:3 2.61 92.8 Green 382 Example 321 1-133:2-32 1:1 3.25 87.3 Green 379 Example 322 1:2 3.22 86.2 Green 382 Example 323 1:3 3.13 85.5 Green 388 Example 324 1-136:2-34 1:1 3.42 92.3 Green 346 Example 325 1:2 3.41 91.6 Green 356 Example 326 1:3 3.39 90.7 Green 369 Example 327 1-140:2-32 1:1 3.05 89.3 Green 366 Example 328 1:2 3.01 88.7 Green 372 Example 329 1:3 2.98 87.1 Green 375 Example 330 1-144:2-33 1:1 3.13 93.5 Green 349 Example 331 1:2 3.11 92.7 Green 352 Example 332 1:3 3.04 92.1 Green 362 Example 333 1-145:2-34 1:1 3.18 90.8 Green 348 Example 334 1:2 3.15 89.7 Green 352 Example 335 1:3 3.05 88.3 Green 362 Example 336 1-146:2-23 1:1 3.23 87.9 Green 395 Example 337 1:2 3.20 86.3 Green 400 Example 338 1:3 3.14 85.5 Green 402

Example 339 1-148:2-23 1:1 3.33 88.3 Green 268 Example 340 1:2 3.31 87.4 Green 272 Example 341 1:3 3.28 87.2 Green 279 Example 342 1-150:2-32 1:1 3.36 91.3 Green 278 Example 343 1:2 3.32 90.5 Green 283 Example 344 1:3 3.28 89.3 Green 288 Example 345 1-154:2-32 1:1 3.42 92.0 Green 293 Example 346 1:2 3.38 91.8 Green 299 Example 347 1:3 3.32 91.1 Green 307 Example 348 1-160 : 2-34 1:1 3.26 89.9 Green 313 Example 349 1:2 3.21 88.3 Green 328 Example 350 1:3 3.16 88.0 Green 339 Example 351 1-161:2-42 1:1 3.22 87.9 Green 308 Example 352 1:2 3.16 87.5 Green 312 Example 353 1:3 3.07 87.0 Green 329 Example 354 1-166:2-42 1:1 3.34 88.3 Green 333 Example 355 1:2 3.31 87.2 Green 342 Example 356 1:3 3.29 86.9 Green 348 Example 357 1-171:2-33 1:1 3.32 87.9 Green 326 Example 358 1:2 3.28 87.7 Green 335 Example 359 1:3 3.25 86.5 Green 342 Example 360 1-176:2-42 1:1 3.22 86.9 Green 348 Example 361 1:2 3.16 86.3 Green 352 Example 362 1:3 3.03 85.2 Green 355 Example 363 1-189:2-44 1:1 2.66 91.6 Green 361 Example 364 1:2 2.61 90.9 Green 368 Example 365 1:3 2.58 89.7 Green 372 Example 366 1-190 : 2-34 1:1 2.59 93.2 Green 355 Example 367 1:2 2.55 92.8 Green 362 Example 368 1:3 2.51 92.0 Green 372 Example 369 1-192:2-32 1:1 2.63 94.4 Green 375 Example 370 1:2 2.60 93.2 Green 378 Example 371 1:3 2.57 92.8 Green 382 Example 372 1-193:2-34 1:1 2.58 94.6 Green 346 Example 373 1:2 2.54 93.8 Green 355 Example 374 1:3 2.50 93.3 Green 362 Example 375 1-198:2-34 1:1 2.66 94.7 Green 387 Example 376 1:2 2.62 94.2 Green 389 Example 377 1:3 2.55 93.6 Green 399 Example 378 1-205:2-23 1:1 3.26 90.5 Green 346 Example 379 1:2 3.22 89.2 Green 352 Example 380 1:3 3.15 88.3 Green 396 Example 381 1-212:2-23 1:1 3.35 89.7 Green 387 Example 382 1:2 3.32 88.2 Green 389 Example 383 1:3 3.26 87.3 Green 395 Example 384 1-215:2-34 1:1 3.29 87.2 Green 298 Example 385 1:2 3.25 86.9 Green 305 Example 386 1:3 3.22 86.1 Green 312 Example 387 1-216:2-42 1:1 3.38 85.7 Green 322 Example 388 1:2 3.35 85.0 Green 338 Example 389 1:3 3.31 84.4 Green 342 Example 390 1-217:2-42 1:1 3.34 90.8 Green 329 Example 391 1:2 3.31 89.7 Green 335 Example 392 1:3 3.26 88.5 Green 342 Example 393 1-221:2-42 1:1 3.35 91.2 Green 359 Example 394 1:2 3.31 90.7 Green 362 Example 395 1:3 3.29 90.0 Green 366 Example 396 1-222:2-44 1:1 3.26 89.7 Green 365 Example 397 1:2 3.22 88.3 Green 372 Example 398 1:3 3.18 87.7 Green 388 Example 399 1-232:2-33 1:1 3.38 89.3 Green 286 Example 400 1:2 3.34 88.1 Green 291 Example 401 1:3 3.31 87.2 Green 299 Example 402 1-236:2-42 1:1 3.33 87.9 Green 305 Example 403 1:2 3.29 87.3 Green 312 Example 404 1:3 3.21 86.5 Green 320 Example 405 1-239:2-34 1:1 3.36 88.5 Green 344 Example 406 1:2 3.31 88.1 Green 351 Example 407 1:3 3.26 87.6 Green 355 Example 408 1-244:2-23 1:1 3.42 87.9 Green 269 Example 409 1:2 3.38 87.3 Green 272 Example 410 1:3 3.32 86.7 Green 283 Example 411 1-257:2-23 1:1 2.66 95.3 Green 277 Example 412 1:2 2.64 94.7 Green 283 Example 413 1:3 2.61 94.3 Green 291 Example 414 1-262:2-33 1:1 2.57 94.5 Green 264 Example 415 1:2 2.53 94.2 Green 273 Example 416 1:3 2.50 93.8 Green 281 Example 417 1-268:2-42 1:1 2.58 94.7 Green 259 Example 418 1:2 2.54 94.0 Green 261 Example 419 1:3 2.51 93.7 Green 266 Example 420 1-277:2-42 1:1 2.66 88.5 Green 321 Example 421 1:2 2.63 88.2 Green 338 Example 422 1:3 2.56 87.3 Green 342 Example 423 1-278:2-44 1:1 3.06 87.9 Green 333 Example 424 1:2 2.99 87.2 Green 346 Example 425 1:3 2.87 86.3 Green 352 Example 426 1-280 : 2-34 1:1 3.13 88.2 Green 316 Example 427 1:2 3.09 87.2 Green 322 Example 428 1:3 2.85 86.9 Green 339 Example 429 1-283:2-34 1:1 3.23 85.7 Green 343 Example 430 1:2 3.16 84.1 Green 350 Example 431 1:3 3.11 84.0 Green 352 Example 432 1-287:2-32 1:1 3.42 86.7 Green 361 Example 433 1:2 3.40 86.3 Green 363 Example 434 1:3 3.38 85.5 Green 369 Example 435 1-289:2-32 1:1 3.15 88.5 Green 342 Example 436 1:2 3.12 87.6 Green 344 Example 437 1:3 3.07 87.1 Green 352 Example 438 1-294:2-42 1:1 3.33 89.3 Green 349 Example 439 1:2 3.30 88.2 Green 352 Example 440 1:3 3.27 87.9 Green 355 Example 441 1-296:2-42 1:1 3.29 88.3 Green 400 Example 442 1:2 3.25 87.9 Green 406 Example 443 1:3 3.22 86.1 Green 411 Example 444 1-300 : 2-34 1:1 3.33 86.4 Green 388 Example 445 1:2 3.29 85.1 Green 391 Example 446 1:3 3.22 84.4 Green 399 Example 447 1-304:2-44 1:1 3.42 89.3 Green 420 Example 448 1:2 3.40 88.2 Green 422 Example 449 1:3 3.39 87.7 Green 435 Example 450 1-311:2-23 1:1 3.34 85.6 Green 446 Example 451 1:2 3.31 84.7 Green 450 Example 452 1:3 3.26 83.2 Green 451 Example 453 1-313:2-32 1:1 3.39 90.5 Green 369 Example 454 1:2 3.35 89.4 Green 371 Example 455 1:3 3.31 88.1 Green 373 Example 456 1-329:2-32 1:1 2.87 95.7 Green 383 Example 457 1:2 2.77 94.3 Green 385 Example 458 1:3 2.73 93.7 Green 391

Example 459 1-334:2-34 1:1 2.61 96.6 Green 376 Example 460 1:2 2.59 96.1 Green 383 Example 461 1:3 2.55 95.8 Green 391 Example 462 1-340:2-33 1:1 2.63 95.7 Green 382 Example 463 1:2 2.59 95.5 Green 391 Example 464 1:3 2.54 94.7 Green 399 Example 465 1-349:2-23 1:1 3.26 91.6 Green 403 Example 466 1:2 3.22 90.3 Green 413 Example 467 1:3 3.16 89.2 Green 422 Example 468 1-356:2-32 1:1 3.34 87.6 Green 432 Example 469 1:2 3.32 87.2 Green 435 Example 470 1:3 3.29 86.1 Green 446 Example 471 1-360:2-23 1:1 3.42 93.3 Green 428 Example 472 1:2 3.36 92.1 Green 432 Example 473 1:3 3.32 91.0 Green 439 Example 474 1-361:2-32 1:1 3.31 89.7 Green 369 Example 475 1:2 3.26 88.8 Green 372 Example 476 1:3 3.21 87.7 Green 385 Example 477 1-365:2-33 1:1 3.36 88.3 Green 316 Example 478 1:2 3.31 87.0 Green 326 Example 479 1:3 3.26 86.4 Green 339 Example 480 1-368:2-34 1:1 3.42 93.4 Green 328 Example 481 1:2 3.36 92.7 Green 339 Example 482 1:3 3.32 91.6 Green 341 Example 483 1-374:2-23 1:1 3.44 95.4 Green 328 Example 484 1:2 3.41 94.2 Green 336 Example 485 1:3 3.38 93.0 Green 342 Example 486 1-382:2-32 1:1 3.31 92.7 Green 308 Example 487 1:2 3.29 91.6 Green 316 Example 488 1:3 3.26 89.7 Green 329 Example 489 1-384:2-23 1:1 3.42 90.7 Green 325 Example 490 1:2 3.39 89.3 Green 339 Example 491 1:3 3.35 88.2 Green 342 Example 492 1-388:2-44 1:1 3.44 89.7 Green 382 Example 493 1:2 3.42 88.3 Green 391 Example 494 1:3 3.38 87.4 Green 402 Example 495 1-401:2-23 1:1 2.62 92.7 Green 413 Example 496 1:2 2.58 92.1 Green 423 Example 497 1:3 2.54 91.9 Green 439 Example 498 1-407:2-34 1:1 2.66 93.7 Green 441 Example 499 1:2 2.61 93.3 Green 450 Example 500 1:3 2.59 92.7 Green 455 Example 501 1-411:2-33 1:1 2.57 94.8 Green 391 Example 502 1:2 2.55 94.2 Green 402 Example 503 1:3 2.46 93.7 Green 413 Example 504 1-422:2-34 1:1 3.34 89.7 Green 412 Example 505 1:2 3.32 88.3 Green 423 Example 506 1:3 3.26 87.2 Green 433 Example 507 1-426:2-42 1:1 3.39 91.1 Green 429 Example 508 1:2 3.35 90.5 Green 430 Example 509 1:3 3.31 89.7 Green 433 Example 510 1-432:2-34 1:1 3.40 92.7 Green 428 Example 511 1:2 3.38 91.6 Green 432 Example 512 1:3 3.34 90.1 Green 439 Example 513 1-433:2-34 1:1 3.40 92.2 Green 368 Example 514 1:2 3.34 91.5 Green 371 Example 515 1:3 3.32 90.6 Green 382 Example 516 1-437:2-44 1:1 3.29 91.8 Green 383 Example 517 1:2 3.25 90.3 Green 391 Example 518 1:3 3.20 89.6 Green 399 Example 519 1-448:2-44 1:1 3.15 88.3 Green 400 Example 520 1:2 3.11 87.6 Green 410 Example 521 1:3 3.05 86.0 Green 419 Example 522 1-456:2-42 1:1 3.26 87.3 Green 422 Example 523 1:2 3.11 86.6 Green 432 Example 524 1:3 3.06 85.2 Green 439 Example 525 1-474:2-34 1:1 2.63 94.7 Green 435 Example 526 1:2 2.61 94.0 Green 441 Example 527 1:3 2.58 93.5 Green 449 Example 528 1-478:2-32 1:1 2.73 93.7 Green 369 Example 529 1:2 2.71 93.2 Green 371 Example 530 1:3 2.69 92.7 Green 382 Example 531 1-480:2-33 1:1 2.66 95.6 Green 379 Example 532 1:2 2.63 95.1 Green 382 Example 533 1:3 2.59 94.6 Green 391 Example 534 1-493:2-34 1:1 3.23 91.6 Green 388 Example 535 1:2 3.16 90.5 Green 391 Example 536 1:3 3.08 89.7 Green 402 Example 537 1-495:2-42 1:1 3.32 89.3 Green 413 Example 538 1:2 3.26 88.1 Green 423 Example 539 1:3 3.21 87.7 Green 433 Example 540 1-498:2-42 1:1 3.18 88.9 Green 429 Example 541 1:2 3.12 88.1 Green 431 Example 542 1:3 3.06 87.3 Green 444 Example 543 1-510:2-34 1:1 3.23 87.9 Green 426 Example 544 1:2 3.20 87.3 Green 437 Example 545 1:3 3.17 86.0 Green 441 Example 546 1-512:2-42 1:1 3.22 93.2 Green 434 Example 547 1:2 3.16 92.6 Green 442 Example 548 1:3 3.05 91.3 Green 451 Example 549 1-520:2-33 1:1 3.19 90.8 Green 389 Example 550 1:2 3.15 89.2 Green 391 Example 551 1:3 3.10 88.8 Green 403 Example 552 1-532:2-44 1:1 3.22 87.6 Green 413 Example 553 1:2 3.17 86.6 Green 425 Example 554 1:3 3.15 86.1 Green 432 Example 555 1-534:2-33 1:1 3.11 88.6 Green 313 Example 556 1:2 3.08 87.7 Green 326 Example 557 1:3 3.00 86.2 Green 338 Example 558 1-546:2-32 1:1 2.73 96.0 Green 342 Example 559 1:2 2.69 95.5 Green 349 Example 560 1:3 2.65 94.7 Green 352 Example 561 1-551:2-44 1:1 2.58 95.3 Green 362 Example 562 1:2 2.55 94.2 Green 366 Example 563 1:3 2.46 93.7 Green 373 Example 564 1-555:2-33 1:1 2.64 95.7 Green 388 Example 565 1:2 2.61 95.0 Green 391 Example 566 1:3 2.57 94.4 Green 410 Example 567 1-560:2-23 1:1 2.66 95.8 Green 365 Example 568 1:2 2.63 95.2 Green 371 Example 569 1:3 2.59 94.6 Green 377

Example 570 1-568:2-32 1:1 3.19 92.6 Green 369 Example 571 1:2 3.14 91.5 Green 372 Example 572 1:3 3.10 90.4 Green 388 Example 573 1-570:2-32 1:1 3.23 90.7 Green 379 Example 574 1:2 3.19 89.6 Green 383 Example 575 1:3 3.11 88.4 Green 389 Example 576 1-574:2-34 1:1 3.40 87.9 Green 376 Example 577 1:2 3.35 86.6 Green 383 Example 578 1:3 3.32 85.7 Green 391 Example 579 1-577:2-23 1:1 2.44 110.1 Green 443 Example 580 1:2 2.41 109.2 Green 452 Example 581 1:3 2.39 108.3 Green 456 Example 582 1-580:2-34 1:1 2.38 108.3 Green 438 Example 583 1:2 2.35 105.2 Green 442 Example 584 1:3 2.31 104.1 Green 449 Example 585 1-583:2-42 1:1 2.42 113.2 Green 439 Example 586 1:2 2.39 112.6 Green 442 Example 587 1:3 2.35 111.1 Green 449 Example 588 1-598:2-44 1:1 2.46 112.3 Green 453 Example 589 1:2 2.44 111.7 Green 459 Example 590 1:3 2.41 110.8 Green 463 Example 591 1-600 : 2-34 1:1 2.38 106.2 Green 502 Example 592 1:2 2.35 105.5 Green 513 Example 593 1:3 2.31 104.7 Green 522 Example 594 1-617:2-34 1:1 2.14 118.8 Green 528 Example 595 1:2 2.11 117.6 Green 531 Example 596 1:3 2.08 116.2 Green 539 Example 597 1-620:2-42 1:1 2.19 115.7 Green 467 Example 598 1:2 2.15 114.6 Green 477 Example 599 1:3 2.11 113.8 Green 482 Example 600 1-623:2-44 1:1 2.25 113.5 Green 459 Example 601 1:2 2.22 112.1 Green 469 Example 602 1:3 2.19 111.3 Green 477 Example 603 1-628:2-33 1:1 2.21 122.3 Green 485 Example 604 1:2 2.16 121.3 Green 493 Example 605 1:3 2.10 120.7 Green 502 Example 606 1-637:2-23 1:1 2.44 111.7 Green 513 Example 607 1:2 2.41 110.2 Green 522 Example 608 1:3 2.36 109.9 Green 539 Example 609 1-642:2-34 1:1 2.50 110.8 Green 546 Example 610 1:2 2.49 109.7 Green 555 Example 611 1:3 2.44 108.8 Green 559 Example 612 1-644:2-23 1:1 2.47 107.7 Green 468 Example 613 1:2 2.42 106.5 Green 471 Example 614 1:3 2.36 105.1 Green 474 Example 615 1-647:2-23 1:1 2.44 111.8 Green 483 Example 616 1:2 2.38 110.7 Green 489 Example 617 1:3 2.31 108.6 Green 492 Example 618 1-653:2-32 1:1 2.47 109.9 Green 487 Example 619 1:2 2.46 108.4 Green 492 Example 620 1:3 2.36 107.1 Green 500 Example 621 1-655:2-32 1:1 2.42 110.6 Green 487 Example 622 1:2 2.36 110.0 Green 492 Example 623 1:3 2.33 109.9 Green 503 Example 624 1-659:2-23 1:1 2.41 108.7 Green 513 Example 625 1:2 2.37 107.1 Green 522 Example 626 1:3 2.35 106.6 Green 539 Example 627 1-670:2-23 1:1 2.46 108.3 Green 468 Example 628 1:2 2.41 107.7 Green 472 Example 629 1:3 2.36 106.5 Green 477 Example 630 1-690:2-33 1:1 2.16 116.5 Green 483 Example 631 1:2 2.11 115.1 Green 485 Example 632 1:3 2.06 114.6 Green 491 Example 633 1-692:2-34 1:1 2.32 113.7 Green 492 Example 634 1:2 2.26 112.6 Green 502 Example 635 1:3 2.21 111.3 Green 513 Example 636 1-693:2-23 1:1 2.27 117.6 Green 523 Example 637 1:2 2.25 116.3 Green 533 Example 638 1:3 2.21 115.2 Green 546 Example 639 1-699:2-34 1:1 2.23 118.7 Green 526 Example 640 1:2 2.16 117.6 Green 538 Example 641 1:3 2.10 115.5 Green 546 Example 642 1-710:2-34 1:1 2.47 113.5 Green 535 Example 643 1:2 2.44 112.8 Green 559 Example 644 1:3 2.32 111.2 Green 560 Example 645 1-713:2-42 1:1 2.36 113.3 Green 513 Example 646 1:2 2.33 112.6 Green 522 Example 647 1:3 2.26 111.7 Green 538 Example 648 1-718:2-42 1:1 2.33 113.3 Green 468 Example 649 1:2 2.31 110.6 Green 472 Example 650 1:3 2.26 109.1 Green 483 Example 651 1-721:2-33 1:1 2.44 108.7 Green 477 Example 652 1:2 2.42 107.7 Green 482 Example 653 1:3 2.36 106.2 Green 493 Example 654 1-728:2-23 1:1 2.38 112.3 Green 472 Example 655 1:2 2.32 111.6 Green 475 Example 656 1:3 2.29 110.7 Green 484 Example 657 1-731:2-23 1:1 2.39 113.3 Green 462 Example 658 1:2 2.35 112.6 Green 465 Example 659 1:3 2.26 111.1 Green 473 Example 660 1-740:2-32 1:1 2.46 113.7 Green 452 Example 661 1:2 2.44 112.2 Green 463 Example 662 1:3 2.40 111.3 Green 477 Example 663 1-741:2-23 1:1 2.29 112.6 Green 426 Example 664 1:2 2.25 111.0 Green 438 Example 665 1:3 2.21 109.8 Green 442 Example 666 1-748:2-33 1:1 2.33 108.7 Green 416 Example 667 1:2 2.31 107.7 Green 426 Example 668 1:3 2.26 106.5 Green 432 Example 669 1-761:2-42 1:1 2.21 118.7 Green 429 Example 670 1:2 2.16 116.2 Green 433 Example 671 1:3 2.15 115.6 Green 449 Example 672 1-763:2-42 1:1 2.25 120.3 Green 418 Example 673 1:2 2.22 119.6 Green 425 Example 674 1:3 2.16 118.3 Green 431 Example 675 1-768:2-44 1:1 2.23 118.6 Green 428 Example 676 1:2 2.21 117.7 Green 432 Example 677 1:3 2.16 116.2 Green 449 Example 678 1-783:2-34 1:1 2.41 107.3 Green 411 Example 679 1:2 2.36 105.2 Green 425 Example 680 1:3 2.33 104.4 Green 439 Example 681 1-786:2-32 1:1 2.40 110.6 Green 426 Example 682 1:2 2.38 108.5 Green 433 Example 683 1:3 2.33 107.3 Green 449 Example 684 1-791:2-33 1:1 2.37 106.5 Green 406 Example 685 1:2 2.32 105.2 Green 413 Example 686 1:3 2.29 104.4 Green 426 Example 687 1-797:2-42 1:1 2.43 111.3 Green 500 Example 688 1:2 2.40 110.6 Green 513 Example 689 1:3 2.37 109.3 Green 526

Example 690 1-804:2-44 1:1 2.55 108.7 Green 523 Example 691 1:2 2.51 107.2 Green 531 Example 692 1:3 2.46 106.6 Green 542 Example 693 1-810:2-23 1:1 2.47 106.8 Green 498 Example 694 1:2 2.44 105.2 Green 503 Example 695 1:3 2.41 104.4 Green 513 Example 696 1-814:2-32 1:1 2.49 112.3 Green 487 Example 697 1:2 2.46 111.6 Green 492 Example 698 1:3 2.37 110.1 Green 499 Example 699 1-819:2-23 1:1 2.38 113.7 Green 476 Example 700 1:2 2.35 112.5 Green 482 Example 701 1:3 2.31 111.2 Green 492 Example 702 1-829:2-33 1:1 2.21 120.0 Green 488 Example 703 1:2 2.18 119.5 Green 491 Example 704 1:3 2.15 118.7 Green 501 Example 705 1-832:2-34 1:1 2.30 118.6 Green 467 Example 706 1:2 2.29 117.2 Green 472 Example 707 1:3 2.25 115.7 Green 483 Example 708 1-836:2-44 1:1 2.26 117.9 Green 477 Example 709 1:2 2.22 116.2 Green 482 Example 710 1:3 2.17 115.7 Green 493 Example 711 1-842:2-33 1:1 3.37 110.2 Green 500 Example 712 1:2 2.35 108.7 Green 513 Example 713 1:3 2.31 107.3 Green 526 Example 714 1-848:2-32 1:1 2.43 105.2 Green 413 Example 715 1:2 2.41 104.0 Green 426 Example 716 1:3 2.38 102.7 Green 438 Example 717 1-853:2-34 1:1 2.43 125.5 Green 456 Example 718 1:2 2.41 124.7 Green 462 Example 719 1:3 2.38 123.1 Green 471 Example 720 1-859:2-42 1:1 2.39 124.6 Green 473 Example 721 1:2 2.35 123.7 Green 475 Example 722 1:3 2.33 122.9 Green 477 Example 723 1-864:2-44 1:1 2.55 115.2 Green 468 Example 724 1:2 2.51 114.8 Green 472 Example 725 1:3 2.48 113.7 Green 483 Example 726 1-867:2-34 1:1 2.47 123.6 Green 501 Example 727 1:2 2.44 122.1 Green 513 Example 728 1:3 2.41 121.5 Green 522 Example 729 1-869:2-44 1:1 2.50 118.7 Green 532 Example 730 1:2 2.47 115.2 Green 546 Example 731 1:3 2.42 112.3 Green 553 Example 732 1-877:2-32 1:1 2.44 129.5 Green 468 Example 733 1:2 2.38 128.4 Green 471 Example 734 1:3 2.31 127.1 Green 482 Example 735 1-891:2-34 1:1 2.25 126.7 Green 483 Example 736 1:2 2.22 125.3 Green 488 Example 737 1:3 2.16 124.7 Green 491 Example 738 1-894:2-32 1:1 2.23 127.8 Green 472 Example 739 1:2 2.20 126.1 Green 477 Example 740 1:3 2.16 125.6 Green 483 Example 741 1-896:2-23 1:1 2.36 126.3 Green 485 Example 742 1:2 2.31 125.1 Green 491 Example 743 1:3 2.26 124.6 Green 499 Example 744 1-899:2-42 1:1 2.16 127.9 Green 500 Example 745 1:2 2.11 126.1 Green 513 Example 746 1:3 2.08 125.5 Green 529 Example 747 1-905:2-42 1:1 2.46 116.7 Green 531 Example 748 1:2 2.44 115.2 Green 539 Example 749 1:3 2.42 114.6 Green 546 Example 750 1-908:2-23 1:1 2.38 121.3 Green 547 Example 751 1:2 2.35 120.6 Green 559 Example 752 1:3 2.31 119.5 Green 560 Example 753 1-910:2-32 1:1 2.47 118.7 Green 503 Example 754 1:2 2.45 117.6 Green 513 Example 755 1:3 2.44 116.3 Green 529 Example 756 1-917:2-32 1:1 2.49 120.5 Green 513 Example 757 1:2 2.45 119.3 Green 529 Example 758 1:3 2.41 118.7 Green 532 Example 759 1-923:2-23 1:1 2.38 123.5 Green 546 Example 760 1:2 2.33 122.6 Green 552 Example 761 1:3 2.25 121.8 Green 560 Example 762 1-927:2-33 1:1 2.42 119.5 Green 487 Example 763 1:2 2.39 118.1 Green 491 Example 764 1:3 2.33 117.0 Green 499 Example 765 1-935:2-23 1:1 2.37 120.3 Green 476 Example 766 1:2 2.35 119.5 Green 483 Example 767 1:3 2.24 117.2 Green 491 Example 768 1-945:2-32 1:1 2.11 123.9 Green 459 Example 769 1:2 2.08 122.7 Green 462 Example 770 1:3 2.05 121.1 Green 473 Example 771 1-947:2-23 1:1 2.23 128.7 Green 475 Example 772 1:2 2.16 127.1 Green 479 Example 773 1:3 2.11 126.0 Green 483 Example 774 1-962:2-33 1:1 2.61 118.7 Green 456 Example 775 1:2 2.50 117.2 Green 462 Example 776 1:3 2.44 116.5 Green 471 Example 777 1-964:2-42 1:1 2.43 120.3 Green 462 Example 778 1:2 2.40 118.5 Green 468 Example 779 1:3 2.33 117.2 Green 472 Example 780 1-966:2-32 1:1 2.41 119.3 Green 481 Example 781 1:2 2.37 118.2 Green 488 Example 782 1:3 2.35 117.5 Green 491 Example 783 1-970:2-42 1:1 2.33 115.2 Green 487 Example 784 1:2 2.31 114.8 Green 491 Example 785 1:3 2.29 111.9 Green 503 Example 786 1-976:2-44 1:1 2.38 120.1 Green 511 Example 787 1:2 2.34 119.7 Green 526 Example 788 1:3 2.31 115.6 Green 538 Example 789 1-980:2-33 1:1 2.51 118.3 Green 533 Example 790 1:2 2.49 117.1 Green 542 Example 791 1:3 2.44 115.8 Green 550 Example 792 1-984:2-23 1:1 2.56 119.5 Green 450 Example 793 1:2 2.51 117.2 Green 456 Example 794 1:3 2.49 116.8 Green 469

Example 795 1-989:2-32 1:1 2.16 130.0 Green 458 Example 796 1:2 2.11 129.7 Green 463 Example 797 1:3 2.05 128.1 Green 472 Example 798 1-994:2-34 1:1 2.32 127.6 Green 475 Example 799 1:2 2.26 126.3 Green 483 Example 800 1:3 2.21 125.5 Green 491 Example 801 1-998:2-34 1:1 2.27 128.7 Green 463 Example 802 1:2 2.25 127.2 Green 471 Example 803 1:3 2.21 126.1 Green 482 Example 804 1-1002:2-23 1:1 2.62 122.5 Green 477 Example 805 1:2 2.58 121.7 Green 489 Example 806 1:3 2.51 120.3 Green 491 Example 807 1-1007:2-34 1:1 2.46 121.9 Green 487 Example 808 1:2 2.41 120.5 Green 493 Example 809 1:3 2.38 119.7 Green 500 Example 810 1-1012:2-42 1:1 2.39 118.7 Green 462 Example 811 1:2 2.35 117.6 Green 477 Example 812 1:3 2.31 116.2 Green 483 Example 813 1-1017:2-44 1:1 2.35 118.5 Green 472 Example 814 1:2 2.31 117.2 Green 485 Example 815 1:3 2.26 116.1 Green 491 Example 816 1-1020:2-34 1:1 2.44 120.5 Green 462 Example 817 1:2 2.41 119.7 Green 473 Example 818 1:3 2.38 118.5 Green 482 Example 819 1-1032:2-34 1:1 2.39 117.8 Green 477 Example 820 1:2 2.35 116.2 Green 486 Example 821 1:3 2.31 115.3 Green 492 Example 822 1-1036:2-33 1:1 2.44 116.7 Green 480 Example 823 1:2 2.41 115.3 Green 491 Example 824 1:3 2.36 112.7 Green 503 Example 825 1-1042:2-44 1:1 2.33 128.7 Green 479 Example 826 1:2 2.26 127.2 Green 483 Example 827 1:3 2.21 126.1 Green 499 Example 828 1-1044:2-23 1:1 2.32 126.5 Green 472 Example 829 1:2 2.26 125.8 Green 483 Example 830 1:3 2.22 124.3 Green 491 Example 831 1-1046:2-23 1:1 2.25 127.9 Green 463 Example 832 1:2 2.21 126.5 Green 472 Example 833 1:3 2.17 125.1 Green 483 Example 834 1-1049:2-34 1:1 2.44 123.7 Green 488 Example 835 1:2 2.42 122.6 Green 491 Example 836 1:3 2.40 121.5 Green 500 Example 837 1-1055:2-34 1:1 2.50 118.5 Green 463 Example 838 1:2 2.49 114.2 Green 475 Example 839 1:3 2.44 112.6 Green 482 Example 840 1-1057:2-32 1:1 5.15 78.5 Green 168 Example 841 1:2 5.06 77.1 Green 173 Example 842 1:3 4.98 76.2 Green 180 Example 843 1-1064:2-34 1:1 5.08 79.3 Green 130 Example 844 1:2 4.92 78.5 Green 132 Example 845 1:3 4.87 77.6 Green 142 Example 846 1-1067:2-42 1:1 4.88 78.2 Green 139 Example 847 1:2 4.76 77.6 Green 144 Example 848 1:3 4.65 76.1 Green 152 Example 849 1-1072:2-32 1:1 5.35 77.9 Green 163 Example 850 1:2 5.26 76.5 Green 171 Example 851 1:3 5.11 75.2 Green 180 Example 852 1-1102:2-33 1:1 5.29 73.6 Green 177 Example 853 1:2 5.25 72.9 Green 183 Example 854 1:3 5.21 71.5 Green 192 Example 855 1-1108:2-42 1:1 5.38 74.9 Green 135 Example 856 1:2 5.35 73.5 Green 142 Example 857 1:3 5.31 72.9 Green 151 Example 858 1-1118:2-34 1:1 5.46 77.6 Green 146 Example 859 1:2 5.42 76.2 Green 153 Example 860 1:3 5.33 75.7 Green 168 Example 861 1-1149:2-34 1:1 5.49 74.9 Green 149 Example 862 1:2 5.38 73.3 Green 153 Example 863 1:3 5.26 72.6 Green 162 Example 864 1-1156:2-34 1:1 5.39 77.9 Green 166 Example 865 1:2 5.33 76.1 Green 175 Example 866 1:3 5.31 75.2 Green 182 Example 867 1-1162:2-32 1:1 5.26 78.3 Green 135 Example 868 1:2 5.22 77.1 Green 142 Example 869 1:3 5.17 76.0 Green 159

Example 870 1-1178:2-33 1:1 4.62 85.0 Green 160 Example 871 1:2 4.55 84.6 Green 172 Example 872 1:3 4.51 83.7 Green 183 Example 873 1-1180:2-32 1:1 4.66 84.9 Green 188 Example 874 1:2 4.59 83.6 Green 193 Example 875 1:3 4.56 82.8 Green 200 Example 876 1-1200 : 2-42 1:1 5.23 77.9 Green 179 Example 877 1:2 5.16 76.2 Green 183 Example 878 1:3 5.11 75.1 Green 192 Example 879 1-1206:2-44 1:1 5.35 75.9 Green 188 Example 880 1:2 5.31 74.3 Green 193 Example 881 1:3 5.28 73.4 Green 203 Example 882 1-1222:2-33 1:1 4.66 85.0 Green 172 Example 883 1:2 4.61 84.6 Green 183 Example 884 1:3 4.58 83.2 Green 192 Example 885 1-1228:2-42 1:1 4.63 84.6 Green 182 Example 886 1:2 4.61 83.7 Green 193 Example 887 1:3 4.59 82.5 Green 200 Example 888 1-1249:2-34 1:1 4.50 84.7 Green 215 Example 889 1:2 4.48 83.5 Green 223 Example 890 1:3 4.42 82.6 Green 231 Example 891 1-1254:2-42 1:1 4.45 75.9 Green 241 Example 892 1:2 4.38 74.2 Green 245 Example 893 1:3 4.33 73.2 Green 253 Example 894 1-1263:2-32 1:1 4.34 75.5 Green 168 Example 895 1:2 4.31 74.2 Green 173 Example 896 1:3 4.25 73.6 Green 188 Example 897 1-1284:2-32 1:1 4.50 74.9 Green 182 Example 898 1:2 4.48 74.4 Green 193 Example 899 1:3 4.36 73.1 Green 205 Example 900 1-1288:2-42 1:1 4.47 72.8 Green 213 Example 901 1:2 4.45 71.6 Green 229 Example 902 1:3 4.38 70.5 Green 235 Example 903 1-1296:2-34 1:1 4.51 80.6 Green 231 Example 904 1:2 4.44 79.8 Green 243 Example 905 1:3 4.35 78.2 Green 250 Example 906 1-1313:2-32 1:1 4.59 79.5 Green 187 Example 907 1:2 4.51 78.2 Green 193 Example 908 1:3 4.48 77.1 Green 203 Example 909 1-1316:2-34 1:1 4.26 76.5 Green 168 Example 910 1:2 4.21 75.1 Green 177 Example 911 1:3 4.18 74.6 Green 185 Example 912 1-1319:2-34 1:1 4.38 73.7 Green 183 Example 913 1:2 4.35 72.1 Green 192 Example 914 1:3 4.31 71.9 Green 203 Example 915 1-1322:2-44 1:1 4.40 73.5 Green 213 Example 916 1:2 4.38 72.4 Green 229 Example 917 1:3 4.33 71.1 Green 236 Example 918 1-1328:2-34 1:1 4.25 78.5 Green 247 Example 919 1:2 4.22 77.6 Green 251 Example 920 1:3 4.19 76.1 Green 255 Example 921 1-1340:2-33 1:1 4.21 84.7 Green 213 Example 922 1:2 4.15 83.5 Green 226 Example 923 1:3 4.11 82.1 Green 237 Example 924 1-1342:2-32 1:1 4.23 85.0 Green 231 Example 925 1:2 4.10 84.7 Green 244 Example 926 1:3 4.09 83.6 Green 259 Example 927 1-1349:2-32 1:1 4.38 71.3 Green 250 Example 928 1:2 4.32 70.6 Green 267 Example 929 1:3 4.29 69.5 Green 271 Example 930 1-1352:2-34 1:1 4.43 73.3 Green 187 Example 931 1:2 4.38 72.5 Green 193 Example 932 1:3 4.31 71.3 Green 203 Example 933 1-1355:2-34 1:1 4.39 75.4 Green 211 Example 934 1:2 4.31 74.2 Green 223 Example 935 1:3 4.28 73.6 Green 238 Example 936 1-1367:2-42 1:1 4.33 74.6 Green 169 Example 937 1:2 4.29 73.3 Green 173 Example 938 1:3 4.21 72.4 Green 182 Example 939 1-1384:2-33 1:1 4.26 76.5 Green 188 Example 940 1:2 4.21 75.1 Green 193 Example 941 1:3 4.19 74.2 Green 215 Example 942 1-1386:2-32 1:1 4.33 77.9 Green 213 Example 943 1:2 4.30 76.2 Green 225 Example 944 1:3 4.27 75.1 Green 237 Example 945 1-1388:2-33 1:1 4.46 78.3 Green 241 Example 946 1:2 4.41 77.2 Green 244 Example 947 1:3 4.33 76.1 Green 250

Compounds A to F used in Comparative Examples 7 to 24 of Table 7 were as follows.

As can be seen from the results of Table 7, the organic light emitting device using the compound represented by Formula 1 and the compound represented by Formula 2 of the present invention as a host of the green organic light emitting device has a driving voltage compared to Comparative Examples 7 to 24. It was confirmed that the light emitting efficiency and lifetime were remarkably improved.

The compound represented by Chemical Formula 1 is an n-type compound, and even when used as a single host, it is a material with excellent lifespan and efficiency of a device, and has an advantage in uniformly depositing organic materials.

In addition, the heterocyclic compound represented by Formula 2 corresponds to a p-type compound.

Therefore, when using an organic material in which a mixture of the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 is used, while an exciplex phenomenon occurs as described below, to uniformly deposit the organic material Since it is easy, the driving voltage is lower than that of Comparative Examples 7 to 24, and the luminous efficiency and lifetime are remarkably improved.

From the results of Table 7, when the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 are used in the organic light emitting device, the performance of the device is higher than when only the heterocyclic compound represented by Formula 1 is used. And it can be confirmed that the lifespan can be increased.

From this result, it can be expected that an exciplex phenomenon occurs when the two compounds are included at the same time. The exciplex phenomenon is an electron exchange between two molecules, and the HOMO level (highest occupied molecular orbital level) of the donor (donor, p-host function) and the LUMO level (lowest unoccupied molecular orbital level) of the acceptor (acceptor, n-host function) level) is a phenomenon in which energy is released.

When the exciplex between two molecules occurs, RISC (Reverse Intersystem Crossing) occurs, and this can increase the internal quantum efficiency of phosphorescence to 100%.

That is, when a donor with good hole transport ability and an acceptor with good electron transport capability are used as the host of the light emitting layer, the driving voltage can be lowered because holes are injected into the p-host and electrons are injected into the n-host. , This can help improve lifespan, which was confirmed from the results of Tables 6 and 7 above.

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 (11)

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 a heterocyclic compound represented by Formula 1 below and An organic light emitting device including a heterocyclic compound represented by Formula 2:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
X is O; or S,
R1 is hydrogen; or deuterium;
Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;
Ar2 and Ar3 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
R2 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;
m is an integer from 0 to 4, and when m is 2 or more, Ar2 in parentheses are the same as or different from each other;
n is an integer from 0 to 2, and when n is 2 or more, Ar3 in parentheses are the same as or different from each other;
m+n≥1, and at least one of Ar2 and Ar3 in parentheses is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
a is an integer from 0 to 7, and when a is 2 or more, R2 in parentheses are the same as or different from each other;
Rc and Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; -SiR31R32R33; -P(=0)R31R32; and a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms and a substituted or unsubstituted amine group. Or, two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,
R21 and R22 are the same as or different from each other, and are each independently -(L)k-SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
L is a direct bond; Or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, k is an integer of 0 to 2, and when k is 2, L in parentheses is the same as or different from each other,
R31, R32, and R33 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
r and s are integers from 0 to 7, and when r and s are integers of 2 or greater, 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 Chemical Formula 3:
[Formula 3]

In Formula 3,
Ar4 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms;
R3 and R4 are the same as or different from each other, and each independently hydrogen; or deuterium;
b is an integer from 0 to 3;
c is an integer from 0 to 2;
When b and c are each 2 or more, the substituents in parentheses are the same as or different from each other,
The definitions of X, R1, R2, Ar1 and a are the same as in Formula 1. The organic light emitting device of claim 1, wherein the content of deuterium in the heterocyclic compound represented by Formula 1 is 10% to 100%. The organic light emitting device of claim 1, wherein the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 is 10% to 100%. 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 Chemical Formula 2 is represented by any one of the following compounds:

The organic light emitting device of claim 1, wherein the organic material layer includes one or more light emitting layers, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2. A composition for an organic material layer of 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,
X is O; or S,
R1 is hydrogen; or deuterium;
Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;
Ar2 and Ar3 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
R2 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;
m is an integer from 0 to 4, and when m is 2 or more, Ar2 in parentheses are the same as or different from each other;
n is an integer from 0 to 2, and when n is 2 or more, Ar3 in parentheses are the same as or different from each other;
m+n≥1, and at least one of Ar2 and Ar3 in parentheses is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
a is an integer from 0 to 7, and when a is 2 or more, R2 in parentheses are the same as or different from each other;
Rc and Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; -SiR31R32R33; -P(=0)R31R32; and a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms and a substituted or unsubstituted amine group selected from the group consisting of Or, two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,
R21 and R22 are the same as or different from each other, and are each independently -(L)k-SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
L is a direct bond; Or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, k is an integer of 0 to 2, and when k is 2, L in parentheses is the same as or different from each other,
R31, R32, and R33 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
r and s are integers from 0 to 7, and when r and s are integers of 2 or greater, the substituents in parentheses are the same as or different from each other. The method according to claim 8, 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 organic material layer composition of the 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 forming of the organic material layer comprises forming one or more organic material layers using the composition for an organic material layer according to claim 8 . The method according to claim 10, wherein the forming of the organic material layer is formed using a thermal vacuum deposition method by pre-mixing the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 Manufacturing an organic light emitting device method.

Images