KR102306986B1 - Heterocyclic compound and organic light emitting device comprising same - Google Patents

Abstract

The present application relates to a heterocyclic compound represented by Formula 1 and an organic light emitting device including the same.

Description

Heterocyclic compound and organic light emitting device comprising the same {HETEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING SAME}

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2019-0074951 filed with the Korean Intellectual Property Office on June 24, 2019, the entire contents of which are incorporated herein by reference.

The present invention relates to a heterocyclic compound represented by Formula 1 and an organic light emitting device comprising the same.

The present invention relates to a heterocyclic compound that can be advantageously used in an organic light emitting device. In particular, the present invention relates to a TADF (thermally activated delayed fluorescence; thermally activated delayed fluorescence) material and its use in an organic light emitting device.

A TADF material is a material in which reverse intersystem crossing (hereinafter, appropriately abbreviated as "RISC") from triplet excitons to singlet excitons can occur. If delayed fluorescence of the TADF material is used, even in fluorescence emission by electric field excitation, an internal quantum efficiency of 100%, which is theoretically equivalent to phosphorescence emission, is possible.

In order for such inverse intersystem crossing to occur, the absolute value (ΔE _ST ) of the difference between the lowest singlet energy level and the lowest triplet energy level is required to be small. That is, in order to express the TADF phenomenon, ΔE _ST of a _{compound must be small, and in order to decrease ΔE ST} , it is necessary to localize the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in a molecule (clearly separated to do) is important.

However, if the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in a molecule are localized without mixing, the π conjugated system in the molecule is reduced or cleaved, making it difficult to be compatible with stability, resulting in light emission This will shorten the life of the device.

Accordingly, development of a compound having a small _{ΔE ST} without degrading other characteristics of the light emitting device is required.

Korean Patent Publication No. 10-2018-0008283

The present invention is to provide a compound that can be used as TADF, since the difference between singlet energy and triplet energy is 0 eV or more and 0.3 eV or less.

In order to solve the above problems, an exemplary embodiment of the present invention provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1,

S1 to S5, S11 to S15, S1' to S5' and S11' to S15' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

a5 is an integer from 0 to 3,

HAr1 is a group represented by the following formula (A),

[Formula A]

In the formula A,

Two of X1 to X3 are N, and the other is N or CR,

R, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

HAr2 is a group represented by the following formula (B),

[Formula B]

In Formula B,

G is hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

b is an integer from 0 to 8, and when b is 2 or more, G is the same as or different from each other,

a1 is 0 or 1,

a2 to a4 are each independently an integer of 0 to 3,

When a3 is 2 or more, HAr1 are the same as or different from each other,

When a4 is 2 or more, HAr2 is the same as or different from each other.

In addition, one embodiment of the present invention is a positive electrode; cathode; and an organic material layer provided between the anode and the cathode, wherein the organic material layer includes the heterocyclic compound described above.

The heterocyclic compound represented by Formula 1 according to an exemplary embodiment of the present invention may be used in an organic material layer of an organic light emitting device, in particular, a light emitting layer.

The organic light emitting diode including the heterocyclic compound represented by Formula 1 according to an exemplary embodiment of the present invention has improved driving voltage, current efficiency, and/or lifespan characteristics.

1 illustrates a structure of an organic light emitting device including a substrate 1 , an anode 2 , an organic material layer 3 , and a cathode 4 .
2 is a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (8), a hole blocking layer (9), an electron transport layer (10) , the structure of the organic light emitting device composed of the electron injection layer 11 and the cathode 4 is illustrated.
3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 8, a layer 12 for injecting and transporting electrons at the same time, and The structure of the organic light emitting device including the cathode 4 is exemplified.
Figure 4 shows the substrate 1, the anode 2, the hole injection layer 5, the hole transport layer 6, the electron blocking layer 7, the light emitting layer 8, the hole blocking layer 9, electron injection and transport The structure of the organic light emitting device composed of the layer 12 and the cathode 4 to be made at the same time is exemplified.

Hereinafter, preferred embodiments of the present invention will be described. However, embodiments of the present invention may be modified differently from the following description, and the scope of the present invention is not limited to the following description. Embodiments of the present invention are provided in order to explain the present invention in detail to those of ordinary skill in the art.

First, before describing some embodiments of the present invention, terms used in the present invention will be described.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

refers to a site bonded to another substituent or a bonding group.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

In the present specification, when an element includes 'X or Y', it means that an element includes X or Y as well as both X and Y.

Examples of substituents in the present specification are described below, but are not limited thereto.

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

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; -Si(Ra)(Rb)(Rc); an alkyl group; cycloalkyl group; -O(Rd); aryl group; And substituted with one or two or more groups selected from the group consisting of a heteroaryl group, or substituted with a group to which two or more of the substituents selected from the group are connected, or one group selected from the group is directly substituted with the atom substituted by the group. group is spiro bonded to each other, or does not have any substituents, and Ra to Rd are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an alkyl group; or an aryl group.

For example, the "group in which two or more groups are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heteroaryl group substituted with an aryl group, an aryl group substituted with an alkyl group, and the like.

In the present specification, the halogen group is a fluoro group (-F); chloro group (-Cl); bromo group (-Br); or iodo group (-I).

In the present specification, the alkyl group refers to a linear or branched saturated hydrocarbon group. In one embodiment, the number of carbon atoms in the alkyl group is 1 to 20; 1 to 15; 1 to 10; or 1 to 6. The alkyl group is specifically methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, Cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1 ,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group means a cyclic saturated hydrocarbon group. The cycloalkyl group may have 3 to 10 carbon atoms. The cycloalkyl group may be specifically a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like, but is not limited thereto.

In the present specification, the aryl group is an aromatic hydrocarbon group; A cyclic group to which an aromatic hydrocarbon is indirectly fused; or a group in which they are linked through a sigma bond. In one embodiment, the carbon number of the aryl group is 6 to 30; 6 to 25; Or it may be 6 to 20, but is not limited thereto.

The aromatic hydrocarbon group refers to a monovalent group of a compound in which all elements have p orbitals and these p orbitals form a conjugate. The aromatic hydrocarbon group may be monocyclic or polycyclic. The monocyclic aromatic hydrocarbon group is specifically a phenyl group, a biphenyl group, etc., and the polycyclic aromatic hydrocarbon group is specifically a naphthyl group, anthracenyl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, phenalenyl group, perylenyl group, chrysenyl group It may be a group, a fluoranthenyl group, etc., but is not limited thereto.

The cyclic group to which the aromatic hydrocarbon is indirectly fused is a direct bond to the aromatic hydrocarbon; Or it means a group connected through an alkylene group, for example, may be a fluorenyl group, etc., but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. In the present specification, the substituted fluorenyl group includes all structures in which two substituents substituted on the pentagonal ring of the fluorenyl group are spiro-bonded with each other to form a ring. The substituted fluorenyl group is a spiro [cyclopentan-1,9'-fluoren]yl group, a 9,9'-spirobi[fluoren]yl group, a 9,9-diphenyl-9H-fluorenyl group, 9,9-dimethyl-9H-fluorenyl group, spiro[fluorene-9,13'-indeno[1,2-l]phenanthrenyl group, etc., but is not limited thereto.

In the present specification, the heteroaryl group refers to a group containing at least one heteroatom selected from the group consisting of N, 0, S, P and Si instead of carbon in the aryl group. In one embodiment, the heteroaryl group has 6 to 30 carbon atoms; 6 to 25; Or it may be 6 to 20, but is not limited thereto.

Examples of the heteroaryl group include a thiophenyl group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridinyl group, a bipyridinyl group, a pyrimidinyl group, a triazinyl group , triazolyl group, acridinyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyra Zinyl group, pyridoindolyl group, benzothienopyrimidinyl group, indenocarbazolyl group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzo Carbazolyl group, benzothiophenyl group, dibenzothiophenyl group, benzofuranyl group, phenanthridinyl group, phenanthrolinyl group, isoxazolyl group, thiadiazolyl group, phenothiazinyl group and dibenzo and a furanyl group, but is not limited thereto.

In the present specification, the triplet energy T1 is a difference value between the energy level of the ground state and the energy level of the triplet excited state.

In the present specification, the singlet energy S1 is a difference value between the energy level of the ground state and the energy level of the singlet excited state.

In the present specification, triplet energy and singlet energy can be measured using a spectrometer capable of measuring fluorescence and phosphorescence.

^{The triplet energy is obtained by preparing a solution at a concentration of 10 -5} M using toluene or tetrahydrofuran (THF) as a solvent in a cryogenic state using liquid nitrogen, and irradiating the solution with a light source in the absorption wavelength band of the material. Except for singlet emission, it can be confirmed by analyzing the triplet emission spectrum. When the electrons are excited from the light source, the time for the electrons to stay at the triplet energy level is much longer than the time for the electrons to stay at the singlet energy level, so it is possible to separate the two components in a cryogenic state.

The singlet energy is measured using a fluorescent device, and unlike the triplet energy level measurement method described above, it can be measured by irradiating a light source at room temperature.

As used herein, "HOMO" is the highest occupied molecular orbital, and "LUMO" is the lowest unoccupied molecular orbital.

As used herein, "energy level" means an energy level. Therefore, even when the energy level is displayed in the negative (-) direction from the vacuum level, the energy level is interpreted as meaning the absolute value of the corresponding energy value. For example, when the energy level is 'large', it means that the absolute value increases in the negative direction from the vacuum level. In addition, in the present specification, expressions such as 'deep' or 'high' of an energy level have the same meaning as an expression of a large energy level.

The HOMO energy level is measured using UV photoelectron spectroscopy (UPS), which irradiates UV on the surface of the thin film, and detects electrons protruding at this time to measure the ionization potential of the material, or the material to be measured It can be measured using cyclic voltammetry (CV), which measures an oxidation potential through a voltage sweep after being dissolved in a solvent together with an electrolyte.

The LUMO energy level may be obtained through inverse photoelectron spectroscopy (IPES) or measurement of an electrochemical reduction potential. In addition to the above method, the LUMO energy level can be calculated using the HOMO energy level and the singlet energy level.

An exemplary embodiment of the present specification provides a heterocyclic compound represented by Formula 1 above.

According to an exemplary embodiment of the present specification, the a1+a2+a3+a4+a5 is 3 or less.

)가 벤젠을 통하여 연결된다. 여기서 상기 시아노기는 전자 받개(electron acceptor)로서 LUMO가 위치하고, 상기 2가의 인돌로카바졸릴기는 전자 주개(electron donor)로서 HOMO가 위치한다. 상기 시아노기와 2가의 인돌로카바졸릴기는 벤젠을 통하여 연결되기 때문에 HOMO와 LUMO가 분리될 수 있고, 이에 상기 화학식 1로 표시되는 헤테로고리 화합물은 지연 형광 특성을 가질 수 있다. The heterocyclic compound represented by Formula 1 has a cyano group and a divalent indolocarbazolyl group (

) is connected via benzene. Here, LUMO is positioned as an electron acceptor in the cyano group, and HOMO is positioned as an electron donor in the divalent indolocarbazolyl group. Since the cyano group and the divalent indolocarbazolyl group are connected through benzene, HOMO and LUMO may be separated, and the heterocyclic compound represented by Formula 1 may have delayed fluorescence properties.

)를 포함하는데, 이에 카바졸-9-일기만을 포함하는 화합물에 비하여 구조적 안정성이 높다. 또한, 카바졸-9-일기에 비하여 이러한 2가의 인돌로카바졸릴는 상대적으로 강한 전자 주개(electron donor)이므로, 발광 파장 및 삼중항 에너지 준위 조절이 용이하여, 이를 통하여 지연 형광 특성을 갖는 고효율 및/또는 장수명의 유기 발광 소자의 구현이 가능하다.In addition, the heterocyclic compound represented by Formula 1 is a divalent indolocarbazolyl group (

), which has high structural stability compared to compounds containing only carbazol-9-yl. In addition, since this divalent indolocarbazolyl is a relatively strong electron donor compared to the carbazol-9-yl group, it is easy to control the emission wavelength and triplet energy level, thereby providing high efficiency with delayed fluorescence properties and / Alternatively, it is possible to implement a long-life organic light emitting device.

In the exemplary embodiment of the present specification, S1 is the same as S11.

In the exemplary embodiment of the present specification, S2 is the same as S12.

In the exemplary embodiment of the present specification, S3 is the same as S13.

In the exemplary embodiment of the present specification, S4 is the same as S14.

In the exemplary embodiment of the present specification, S5 is the same as S15.

In the exemplary embodiment of the present specification, S1' is the same as S11'.

In the exemplary embodiment of the present specification, S2' is the same as S12'.

In the exemplary embodiment of the present specification, S3' is the same as S13'.

In the exemplary embodiment of the present specification, S4' is the same as S14'.

In the exemplary embodiment of the present specification, S5' is the same as S15'.

In the exemplary embodiment of the present specification, S1 is equal to S1', S2 is equal to S2', S3 is equal to S3', S4 is equal to S4', S5 is equal to S5', and S11 is equal to S11'. S12 equals S12', S13 equals S13', S14 equals S14', and S15 equals S15'.

In the exemplary embodiment of the present specification, S1 is equal to S11', S2 is equal to S12', S3 is equal to S13', S4 is equal to S14', S5 is equal to S15', and S11 is equal to S1'. S12 equals S2', S13 equals S3', S14 equals S4', and S15 equals S5'.

In one embodiment of the present specification, the S1 to S5, S11 to S15, S1' to S5' and S11' to S15' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; an alkyl group unsubstituted or substituted with deuterium; Or an aryl group unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, the S1 to S5, S11 to S15, S1' to S5' and S11' to S15' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; _{a C 1-10} alkyl group unsubstituted or substituted with deuterium; _{Or a C 6-20} aryl group unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, the S1 to S5, S11 to S15, S1' to S5' and S11' to S15' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; _{a C 1-10} alkyl group unsubstituted or substituted with deuterium; _{Or a C 6-15} aryl group unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, the S1 to S5, S11 to S15, S1' to S5' and S11' to S15' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; _{a C 1-6} alkyl group unsubstituted or substituted with deuterium; _{Or a C 6-12} aryl group unsubstituted or substituted with deuterium.

In one embodiment of the present specification, the S1 to S5, S11 to S15, S1' to S5' and S11' to S15' are the same as or different from each other, and each independently hydrogen; methyl group; tert-butyl group; phenyl group; or a phenyl group substituted with deuterium.

In an exemplary embodiment of the present specification, S3 and S13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; _{a C 1-6} alkyl group unsubstituted or substituted with deuterium; _{Or a C 6-12} aryl group unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, S3 and S13 are the same as or different from each other, and each independently hydrogen; methyl group; tert-butyl group; phenyl group; or a phenyl group substituted with deuterium.

In an exemplary embodiment of the present specification, S3' and S13' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; _{a C 1-6} alkyl group unsubstituted or substituted with deuterium; _{Or a C 6-12} aryl group unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, S3' and S13' are the same as or different from each other, and each independently hydrogen; methyl group; tert-butyl group; phenyl group; or a phenyl group substituted with deuterium.

According to an exemplary embodiment of the present specification, HAr1 of Formula 1 is represented by Formula A below.

[Formula A]

In the formula A,

Two of X1 to X3 are N, and the other is N or CR,

R, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In an exemplary embodiment of the present specification, X1 to X3 of Formula A are all N.

According to an exemplary embodiment of the present specification, two of X1 to X3 of Formula A are N, and the other is CR.

In an exemplary embodiment of the present specification, R, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; A substituted or unsubstituted C _1-10 alkyl group; a substituted or unsubstituted C _6-20 aryl group; Or a substituted or unsubstituted C _2-20 heteroaryl group.

In an exemplary embodiment of the present specification, R, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted C _1-6 alkyl group; a substituted or unsubstituted C _6-15 aryl group; Or a substituted or unsubstituted C _2-16 heteroaryl group.

In an exemplary embodiment of the present specification, R, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted C _1-6 alkyl group; a substituted or unsubstituted C _6-12 aryl group; Or a substituted or unsubstituted C _2-12 heteroaryl group.

In an exemplary embodiment of the present specification, R, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; an aryl group unsubstituted or substituted with deuterium, an alkyl group, or a cyano group; or a heteroaryl group unsubstituted or substituted with deuterium, an alkyl group, a cyano group, or an aryl group.

In an exemplary embodiment of the present specification, R is hydrogen; heavy hydrogen; or a cyano group.

In an exemplary embodiment of the present specification, R is hydrogen; or a cyano group.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently represents an aryl group unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently represents a phenyl group unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, the formula A is represented by the following formula A-1 or A-2.

[Formula A-1]

[Formula A-2]

In Formulas A-1 and A-2,

The definition of R is as defined in formula A,

Y1 to Y10 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted C _1-6 alkyl group; a substituted or unsubstituted C _6-15 aryl group; Or a substituted or unsubstituted C _2-12 heteroaryl group.

According to an exemplary embodiment of the present specification, Y1 to Y10 are the same as or different from each other, and each independently hydrogen; or deuterium.

According to another exemplary embodiment, Y1 to Y10 are all hydrogen.

According to another exemplary embodiment, Y1 to Y10 are all deuterium.

In an exemplary embodiment of the present specification, HAr2 of Formula 1 is represented by Formula B below.

[Formula B]

In Formula B,

G is hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

b is an integer from 0 to 8, and when b is 2 or more, G is the same as or different from each other.

According to an exemplary embodiment of the present specification, the Chemical Formula B is represented by the following Chemical Formula B-1.

[Formula B-1]

In the formula B-1,

G1 and G2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; A substituted or unsubstituted C _1-10 alkyl group; a substituted or unsubstituted C _6-20 aryl group; Or a substituted or unsubstituted C _2-16 heteroaryl group.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted C _1-6 alkyl group; a substituted or unsubstituted C _6-15 aryl group; Or a substituted or unsubstituted C _2-12 heteroaryl group.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an alkyl group; or an aryl group.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; methyl group; tert-butyl group; or a phenyl group.

In the exemplary embodiment of the present specification, G1 and G2 are the same substituents.

According to an exemplary embodiment of the present specification, G1 and G2 are hydrogen.

According to an exemplary embodiment of the present specification, G1 and G2 are deuterium.

According to an exemplary embodiment of the present specification, G1 and G2 are methyl groups.

According to an exemplary embodiment of the present specification, G1 and G2 are tert-butyl groups.

According to an exemplary embodiment of the present specification, G1 and G2 are a phenyl group.

In an exemplary embodiment of the present specification, G is hydrogen; heavy hydrogen; cyano group; A substituted or unsubstituted C _1-10 alkyl group; a substituted or unsubstituted C _6-20 aryl group; Or a substituted or unsubstituted C _2-16 heteroaryl group.

In an exemplary embodiment of the present specification, G is hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted C _1-6 alkyl group; a substituted or unsubstituted C _6-15 aryl group; Or a substituted or unsubstituted C _2-12 heteroaryl group.

In an exemplary embodiment of the present specification, G is hydrogen; heavy hydrogen; an alkyl group; or an aryl group.

In an exemplary embodiment of the present specification, G is hydrogen; heavy hydrogen; methyl group; tert-butyl group; or a phenyl group.

In the exemplary embodiment of the present specification, b is an integer of 0 to 8, and when b is 2 or more, two or more Gs are the same as or different from each other.

According to another exemplary embodiment, b is 1 or 2, and when b is 2, two Gs are the same as or different from each other.

According to an exemplary embodiment of the present specification, a1 is 0 or 1.

In the exemplary embodiment of the present specification, when a1 is 0, a2+a3+a4+a5 is an integer of 0 to 3.

According to an exemplary embodiment of the present specification, when a1 is 1, a2+a3+a4+a5 is 0 or 1.

In an exemplary embodiment of the present specification, a2+a3+a4 is 1 or more.

In an exemplary embodiment of the present specification, a2+a3 is 1 or more.

In an exemplary embodiment of the present specification, a2 is 1 or more.

In an exemplary embodiment of the present specification, a3 is 1 or more.

In an exemplary embodiment of the present specification, a4 is 1 or more.

In one embodiment of the present specification, a1 is 0, a2 is 1, a3 is 0, a4 is 2; a1 is 0, a2 is 0, a3 is 1, a4 is 1; a1 is 0, a2 is 0, a3 is 1, a4 is 0; a1 is 1, a2 is 1, a3 is 0, a4 is 0; a1 is 1, a2 is 1, a3 is 0, and a4 is 0.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 1-1 or 1-2.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

S1 to S5, S11 to S15, S1' to S5', S11' to S15', HAr1, HAr2, and a1 to a5 are the same as defined in Formula 1.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 2-1 to 2-3.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,

R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; HAr1; or HAr2,

At least one of R1 to R4 is a cyano group,

At least one of R5 and R6 is a cyano group,

At least one of R7 and R8 is a cyano group,

The definitions of S1 to S5, S11 to S15, S1' to S5', S11' to S15', HAr1 and HAr2 are as defined in Formula 1,

When HAr1 is 2 or more, HAr1 is the same as or different from each other,

When HAr2 is 2 or more, HAr2 is the same as or different from each other.

In an exemplary embodiment of the present specification, R2 is a cyano group.

In an exemplary embodiment of the present specification, R2 and R3 are cyano groups.

In an exemplary embodiment of the present specification, R2 and R4 are cyano groups.

In an exemplary embodiment of the present specification, R1 is a cyano group.

In an exemplary embodiment of the present specification, R1 and R4 are cyano groups.

In an exemplary embodiment of the present specification, R7 is a cyano group.

In an exemplary embodiment of the present specification, R7 and R8 are cyano groups.

In an exemplary embodiment of the present specification, the heterocyclic compound represented by Formula 1 includes at least one deuterium.

In an exemplary embodiment of the present specification, the heterocyclic compound represented by Formula 1 is any one selected from the following compounds.

_{In an exemplary embodiment of the present specification, the difference (ΔE ST} ) between the singlet energy (S1) and the triplet energy (T1) of the heterocyclic compound represented by Formula 1 is 0 eV or more and 0.3 eV or less.

_{According to another exemplary embodiment, the difference (ΔE ST} ) between the singlet energy (S1) and the triplet energy (T1) of the heterocyclic compound represented by Formula 1 is 0 eV or more and 0.2 eV or less.

According to an exemplary embodiment of the present specification, the singlet energy (S1) of the heterocyclic compound represented by Formula 1 is 2 eV or more and 3 eV or less.

According to another exemplary embodiment, the singlet energy (S1) of the heterocyclic compound represented by Formula 1 is 2.3 eV or more and less than 2.6 eV.

According to an exemplary embodiment of the present specification, the triplet energy (T1) of the heterocyclic compound represented by Formula 1 is 2 eV or more and 3 eV or less.

According to another exemplary embodiment, the triplet energy (T1) of the heterocyclic compound represented by Formula 1 is 2.2 eV or more and less than 2.5 eV.

In an exemplary embodiment of the present specification, the HOMO energy level of the heterocyclic compound represented by Formula 1 is 4 eV to 6 eV.

According to an exemplary embodiment of the present specification, the LUMO energy level of the heterocyclic compound represented by Formula 1 is 2 eV to 4 eV.

An exemplary embodiment of the present specification is a positive electrode; cathode; and an organic material layer provided between the anode and the cathode, wherein the organic material layer includes the heterocyclic compound represented by Formula 1 above.

According to an exemplary embodiment of the present specification, the organic material layer including the heterocyclic compound represented by Formula 1 further includes a compound represented by the following Formula 100. In this case, the content of the heterocyclic compound of Formula 1 is 1 part by weight to 60 parts by weight based on 100 parts by weight of the compound represented by Formula 100; 1 to 50 parts by weight; or 1 to 40 parts by weight.

[Formula 100]

In the formula 100,

Cy1 and Cy2 are the same as or different from each other, and each independently represent a substituted or unsubstituted aromatic hydrocarbon ring,

L is a substituted or unsubstituted arylene group,

m is an integer of 1 to 3, and when m is 2 or more, a plurality of substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present specification, Cy1 and Cy2 are the same as or different from each other, and each independently represent a substituted or unsubstituted C _6-20 aromatic hydrocarbon ring.

In another exemplary embodiment, Cy1 and Cy2 are the same as or different from each other, and each independently substituted or unsubstituted benzene; or substituted or unsubstituted naphthalene.

According to another exemplary embodiment, Cy1 and Cy2 are benzene.

According to an exemplary embodiment of the present specification, L is a substituted or unsubstituted C _6-20 arylene group.

In another exemplary embodiment, L is a substituted or unsubstituted phenylene group; or a substituted or unsubstituted biphenylrylene group.

According to another exemplary embodiment, L is a biphenyl rylene group.

According to an exemplary embodiment of the present specification, m is 2.

In an exemplary embodiment of the present specification, the following compound may be mentioned as an example of Chemical Formula 100, but is not limited thereto.

In an exemplary embodiment of the present specification, the organic material layer including the heterocyclic compound represented by Formula 1 further includes a compound represented by Formula 100 and a compound represented by Formula 101 below. At this time, the content of the compound represented by Formula 101 is 1 part by weight to 50 parts by weight based on 100 parts by weight of the total organic layer; 1 to 40 parts by weight; or 1 to 30 parts by weight.

[Formula 101]

In Formula 101,

Cy3 and Cy4 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Y100 is hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

n1 is 1 or 2, and when n1 is 2, a plurality of substituents in parentheses are the same as or different from each other,

n2 is an integer of 0 to 9, and when n2 is 2 or more, a plurality of Y100s are the same as or different from each other.

According to an exemplary embodiment of the present specification, n1 + n2 is an integer of 1 to 10.

In an exemplary embodiment of the present specification, Cy3 and Cy4 are the same as or different from each other, and each independently a substituted or unsubstituted C _6-30 aryl group; Or a substituted or unsubstituted C _2-30 heteroaryl group.

In another exemplary embodiment, Cy3 and Cy4 are the same as or different from each other, and each independently a substituted or unsubstituted C _6-20 aryl group; Or a substituted or unsubstituted C _2-20 heteroaryl group.

According to another exemplary embodiment, Cy3 and Cy4 are the same as or different from each other, and each independently represent a substituted or unsubstituted phenyl group.

In another exemplary embodiment, Cy3 and Cy4 are phenyl groups.

According to an exemplary embodiment of the present specification, n1 is 2.

In an exemplary embodiment of the present specification, Y100 is hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted C _6-30 aryl group; Or a substituted or unsubstituted C _2-30 heteroaryl group.

In another exemplary embodiment, Y100 is hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted C _6-20 aryl group; Or a substituted or unsubstituted C _2-20 heteroaryl group.

According to another exemplary embodiment, the Y100 is hydrogen; heavy hydrogen; or a substituted or unsubstituted phenyl group.

In another exemplary embodiment, Y100 is hydrogen; heavy hydrogen; or a phenyl group.

According to an exemplary embodiment of the present specification, n2 is 2, and two Y100 are the same as or different from each other.

According to an exemplary embodiment of the present specification, Chemical Formula 101 is represented by the following Chemical Formula 101-1.

[Formula 101-1]

In the formula 101-1,

The definitions of Cy3, Cy4 and n1 are the same as in Formula 101,

The definitions of Y101 and Y102 are the same as those of Y100 in Formula 101.

In the exemplary embodiment of the present specification, the following compound may be mentioned as an example of Chemical Formula 101, but is not limited thereto.

In an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Formula 1 above.

In an exemplary embodiment of the present specification, the organic material layer includes an electron injection layer; electron transport layer; a layer that simultaneously injects and transports electrons; or a hole blocking layer, the electron injection layer; electron transport layer; a layer that simultaneously injects and transports electrons; Alternatively, the hole blocking layer includes a heterocyclic compound represented by Formula 1 above.

In an exemplary embodiment of the present specification, the organic material layer includes a hole injection layer; hole transport layer; a layer that simultaneously injects and transports holes; Or including an electron blocking layer, the hole injection layer; hole transport layer; a layer that simultaneously injects and transports holes; Alternatively, the electron blocking layer includes a heterocyclic compound represented by Formula 1 above.

In an exemplary embodiment, the light emitting layer including the heterocyclic compound represented by Formula 1 further includes a host. At this time, the content of the heterocyclic compound of Formula 1 is 1 part by weight to 60 parts by weight based on 100 parts by weight of the host; 1 to 60 parts by weight; or 1 to 40 parts by weight.

In an exemplary embodiment of the present specification, the host may be one or two or more selected from known host compounds such as carbazole-based compounds, and may be a compound represented by Chemical Formula 100 described above. The host is more preferably a compound having a triplet energy higher than the triplet energy level of the heterocyclic compound represented by Formula 1 above. In this case, the triplet energy level of the host is 2.4 eV or more and 3.1 eV or less.

In one embodiment, the light emitting layer including the heterocyclic compound represented by Formula 1 may further include a dopant. At this time, the content of the dopant is 1 part by weight to 50 parts by weight based on 100 parts by weight of the total light emitting layer; 1 to 40 parts by weight; or 1 to 30 parts by weight.

In one embodiment, as the dopant, if the triplet energy level is a compound smaller than the triplet energy level of the heterocyclic compound represented by Formula 1, it may be appropriately selected and used.

In the exemplary embodiment of the present specification, the dopant may be, for example, a pyrene-based, anthracene, or boron-based compound, and may be a compound represented by Chemical Formula 101 described above.

According to an exemplary embodiment of the present specification, the light emitting layer including the heterocyclic compound represented by Formula 1 may further include a host and a dopant. The host may be a compound represented by the aforementioned Chemical Formula 100, and the dopant may be a compound represented by the aforementioned Chemical Formula 101.

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

For example, the structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 to 4 , but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which a substrate 1, an anode 2, an organic material layer 3, and a cathode 4 are sequentially stacked. 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer. In such a structure, the heterocyclic compound represented by Formula 1 may be included in the organic material layer 3 .

2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole injection layer 6, an electron blocking layer 7, a light emitting layer 8, a hole blocking layer 9, an electron transport layer 10 ), the electron injection layer 11 and the cathode 4 are sequentially stacked, the structure of the organic light emitting device is exemplified. In such a structure, the heterocyclic compound represented by Formula 1 may be included in the light emitting layer 8 .

3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole injection layer 6, an electron blocking layer 7, a light emitting layer 8, a layer 12 for injecting and transporting electrons at the same time And the structure of the organic light emitting device in which the cathode 4 is sequentially stacked is exemplified. In such a structure, the heterocyclic compound represented by Formula 1 may be included in the light emitting layer 8 .

4 shows the substrate 1, the anode 2, the hole injection layer 5, the hole transport layer 6, the electron blocking layer 7, the light emitting layer 8, the hole blocking layer 9, electron injection and transport. The structure of the organic light emitting device in which the layer 12 and the cathode 4 are sequentially stacked at the same time is exemplified. In such a structure, the heterocyclic compound represented by Formula 1 may be included in the light emitting layer 8 .

The organic light emitting device of the present specification is manufactured using materials and methods known in the art, except that one or more layers of the organic material layer include the compound of the present specification, that is, the heterocyclic compound represented by Formula 1 above. can be

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate. After forming an anode and forming an organic material layer including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and a layer for simultaneously injecting and transporting electrons thereon, a material that can be used as a cathode It can be prepared by vapor deposition. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode, an organic material layer, and an anode on a substrate. In addition, the compound represented by Formula 1 may be formed into 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 application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

As the anode material, a material having a large work function is generally preferable to facilitate hole injection into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO ₂ : a combination of a metal such as Sb and an oxide; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; LiF/Al or LiO ₂ /Al, and a multi-layered material such as Mg/Ag, but is not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the exciton from moving to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. The hole transport material is a material that can transport holes from the anode or the hole injection layer to the light emitting layer and transfer them to the light emitting layer. material is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The electron blocking layer is a layer that prevents excess electrons passing through the light emitting layer from moving toward the hole transport layer. As the hole control material, a material having a lowest unoccupied molecular orbital (LUMO) level lower than that of the hole transport layer is preferable, and an appropriate material may be selected in consideration of the energy level of the surrounding layer. In an exemplary embodiment, an arylamine-based organic material may be used, but is not limited thereto.

According to an exemplary embodiment of the present specification, the hole transport layer; hole injection layer; electronic blocking layer; Alternatively, the layer that simultaneously injects and transports holes may further include a p-type dopant. As the p-type dopant, those known in the art may be used, and for example, an arylamine-based derivative and a compound including a cyano group may be used. The p-type dopant may be included in an amount of 0.1 wt% to 75 wt%, preferably 30 wt% to 55 wt%, in the electron transport layer, the electron injection layer, or the layer that simultaneously injects and transports electrons.

In the exemplary embodiment of the present specification, the material of the hole injection layer and the hole transport layer may be used for the layer that simultaneously injects and transports holes.

The light emitting material of the light emitting layer is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxyquinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzothiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

In the exemplary embodiment of the present specification, the organic material layer may include two or more light emitting layers, and the two or more light emitting layers may be provided horizontally or vertically.

The emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and hetero ring-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder a furan compound, a pyrimidine derivative, and the like, but is not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, and a metal complex. The aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanthene, and the like, having an arylamino group. The styrylamine compound may be a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine, and one or two or more selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group A substituent may be substituted or unsubstituted. The styrylamine compound includes, but is not limited to, styrylamine, styryldiamine, styryltriamine, and styryltetraamine. Examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The hole blocking layer serves to prevent holes from flowing into the cathode through the light emitting layer during the driving process of the organic light emitting device. As the electron control material, it is preferable to use a material having a very low HOMO (Highest Occupied Molecular Orbital) level. The electron control material may be specifically TPBi, BCP, CBP, PBD, PTCBI, BPhen, etc., but is not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. Suitable. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically, they are cesium, barium, calcium, ytterbium and samarium, followed by an aluminum layer or a silver layer in each case.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect with respect to the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents migration to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

In one embodiment of the present specification, the material of the electron injection layer and the electron transport layer may be used for the layer for simultaneously injecting and transporting electrons.

According to an exemplary embodiment of the present specification, the electron transport layer; electron injection layer; hole blocking layer; Alternatively, the layer for simultaneously injecting and transporting electrons may further include an n-type dopant. As the n-type dopant, those known in the art may be used, for example, alkali metal, alkaline earth metal, alkali metal compound, alkaline earth metal compound, alkali metal complex or alkaline earth metal complex may be used. An oxide, a halide, etc. may be used as the metal compound, and the complex may further include an organic ligand. For example, LiQ or the like may be used. The n-type dopant may be included in an amount of 0.1 wt% to 75 wt%, preferably 30 wt% to 55 wt%, in the electron transport layer, the electron injection layer, or the layer that simultaneously injects and transports electrons.

The organic light emitting device according to the present specification may be a top emission type, a back emission type, or a double side emission type depending on the material used.

< manufacturing example >

The heterocyclic compound of the present invention can be formed by introducing various kinds of substituents to benzene substituted with a cyano group and halide as follows. The heterocyclic compound of the present invention was synthesized through the following Preparation Examples.

manufacturing example 1-1: Synthesis of compound 1-A

After completely dissolving 2,4,5,6-tetrafluoroisophthalonitrile 20g (100mmol) and 11,12-dihydroindolo[2,3-a]carbazole (100mmol) in 200mL of dimethylformamide Sodium-tert-butoxide (210 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid and recrystallized from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 27.9 g of compound 1-A (yield 67%).

MS[M+H]+ = 417

manufacturing example 1-2: Synthesis of compound 1-B

20 g (100 mmol) of 2,4,5,6-tetrafluoroisophthalonitrile and 3,8-dimethyl-11,12-dihydroindolo[2,3-a]carbazole (100 mmol) were mixed with dimethyl After completely dissolving in 200 mL of formamide, sodium-tert-butoxide (210 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid and recrystallized from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 28.9 g of compound 1-B (yield 65%).

MS[M+H]+ = 445

manufacturing example 1-3: Synthesis of compound 1-C

23.3 g (100 mmol) of 3,6-dichloro-4,5-difluorophthalonitrile and 11,12-dihydroindolo [2,3-a] carbazole (100 mmol) were completely dissolved in 200 mL of dimethylformamide After dissolving, sodium-tert-butoxide (210 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid, and recrystallization was performed from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 33.7 g of compound 1-C (yield 75%).

MS[M+H]+ = 449

manufacturing example 1-4: Synthesis of compound 1-D

2,3,5,6-tetrafluoroterephthalonitrile 20g (100mmol) and 11,12-dihydroindolo[2,3-a]carbazole (100mmol) were completely dissolved in 200mL of dimethylformamide and then sodium -tert-butoxide (210 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid, and recrystallization was performed from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 25.8 g of compound 1-D (yield 62%).

MS[M+H]+ = 417

manufacturing example 1-5: Synthesis of compound 1-E

(2-cyano-3,4-difluorophenyl) boronic acid 18.3 g (100 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 110 mmol, tetrahydrofuran Mix 200 mL and 100 mL of water and heat to 60°C. 300 mmol of potassium carbonate and 1 mmol of tetrakistriphenylphosphine palladium were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized with TF/ethanol to obtain 32.2 g of compound 1-E (yield 87%).

MS[M+H]+ = 371

Preparation Example 1-6: Synthesis of compound 1-F

(4-cyano-2,3-difluorophenyl) boronic acid 18.3 g (100 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine in 110 mmol, tetrahydrofuran Mix 200 mL and 100 mL of water and heat to 60°C. 300 mmol of potassium carbonate and 1 mmol of tetrakistriphenylphosphine palladium were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized using TF/ethanol to obtain 33 g of compound 1-F (yield 89%).

MS[M+H]+ = 371

Preparation Example 1-7: Synthesis of compound 1-G

(3-cyano-4,5-difluorophenyl) boronic acid 18.3 g (100 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 110 mmol, tetrahydrofuran Mix 200 mL and 100 mL of water and heat to 60°C. 300 mmol of potassium carbonate and 1 mmol of tetrakistriphenylphosphine palladium were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized with TF/ethanol to obtain 34.4 g of compound 1-G (yield 93%).

MS[M+H]+ = 371

Preparation Example 1-8: Synthesis of compound 1-H

(3-cyano-4,5-difluorophenyl) boronic acid 18.3 g (100 mmol), 4-chloro-2,6-diphenylpyrimidine-5-carbonitrile 110 mmol, tetrahydrofuran 200 mL , mix with 100 mL of water and heat to 60°C. 300 mmol of potassium carbonate and 1 mmol of tetrakistriphenylphosphine palladium were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized with TF/ethanol to obtain 34.3 g of compound 1-H (yield 87%).

MS[M+H]+ = 395

Preparation Example 1-9: Synthesis of compound 1-I

(3-cyano-4,5-difluorophenyl) boronic acid 18.3 g (100 mmol), 2-chloro-4,6-bis (phenyl-d5) -1,3,5-triazine 110 mmol , 200 mL of tetrahydrofuran and 100 mL of water are mixed and heated to 60°C. 300 mmol of potassium carbonate and 1 mmol of tetrakistriphenylphosphine palladium were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized with TF/ethanol to obtain 33.9 g of compound 1-I (yield 89%).

MS[M+H]+ = 381

Preparation Example 2-1: Synthesis of Compound 1

After completely dissolving 1-A 20.8g (50mmol) and 9H-carbazole (110mmol) in 200mL of dimethylformamide, sodium-tert-butoxide (120mmol) was added, and the mixture was heated and stirred at 80°C for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid and recrystallized from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 32.3 g of Compound 1 (yield 91%).

MS[M+H]+ = 711

Preparation 2-2: Synthesis of compound 2

2-A 20.8g (50mmol) and 3,6-dimethyl-9H-carbazole (110mmol) were completely dissolved in 200mL of dimethylformamide, and sodium-tert-butoxide (120mmol) was added thereto, and 80° C. for 6 hours. was heated and stirred. The temperature was lowered to room temperature and filtered to obtain a solid, and recrystallization was performed from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 33.7 g of Compound 2 (yield 88%).

MS[M+H]+ = 767

Preparation 2-3: Synthesis of compound 3

After completely dissolving 1-B 22.2g (50mmol) and 9H-carbazole (110mmol) in 200mL of dimethylformamide, sodium-tert-butoxide (120mmol) was added, and the mixture was heated and stirred at 80°C for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid, and recrystallization was performed from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 33.2 g of compound 3 (yield 90%).

MS[M+H]+ = 739

Preparation 2-4: Synthesis of compound 4

After completely dissolving 1-C 22.5 g (50 mmol) and 3,6-dimethyl-9H-carbazole (110 mmol) in 200 mL of toluene, sodium-tert-butoxide (110 mmol) was added, and tetrakistriphenylphosphine palladium 1 mmol was added and the mixture was stirred under reflux for 1 hour. The temperature was lowered to room temperature and filtered to obtain a solid and recrystallized from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 30.3 g of Compound 4 (yield 79%).

MS[M+H]+ = 767

Preparation Example 2-5: Synthesis of compound 5

2,3,5,6-tetrafluoroterephthalonitrile 10g (50mmol) and 11,12-dihydroindolo[2,3-a]carbazole (110mmol) were completely dissolved in 200mL of dimethylformamide and then sodium -tert-butoxide (120 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid and recrystallized from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 25.6 g of Compound 5 (yield 81%).

MS[M+H]+ = 633

Preparation 2-6: Synthesis of compound 6

After completely dissolving 1-D 20.8g (50mmol) and 9H-carbazole (110mmol) in 200mL of dimethylformamide, sodium-tert-butoxide (120mmol) was added, and the mixture was heated and stirred at 80°C for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid, and recrystallization was performed from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 30.9 g of compound 6 (yield 87%).

MS[M+H]+ = 711

Preparation Example 2-7: Synthesis of compound 7

After completely dissolving 1-E 18.5 g (50 mmol) and 11,12-dihydroindolo [2,3-a] carbazole (50 mmol) in 200 mL of dimethylformamide, sodium-tert-butoxide (110 mmol) was added and , and stirred at 80 °C for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid, and recrystallization was performed from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 23.5 g of Compound 7 (yield 80%).

MS[M+H]+ = 587

Preparation 2-8: Synthesis of compound 8

After completely dissolving 1-F 18.5 g (50 mmol) and 3,8-dimethyl-11,12-dihydroindolo [2,3-a] carbazole (50 mmol) in 200 mL of dimethylformamide, sodium-tert-butoxy Side (110 mmol) was added and heated and stirred at 80° C. for 6 h. The temperature was lowered to room temperature and filtered to obtain a solid, and recrystallization was performed with a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 23.7 g of Compound 8 (yield 77%).

MS[M+H]+ = 615

Preparation 2-9: Synthesis of compound 9

1-G 18.5g (50mmol) and 11,12-dihydroindolo[2,3-a]carbazole (50mmol) were completely dissolved in 200mL of dimethylformamide, and sodium-tert-butoxide (110mmol) was added and , and stirred at 80 °C for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid, and recrystallization was performed from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 22 g of compound 9 (yield 75%).

MS[M+H]+ = 587

Preparation 2-10: Synthesis of compound 10

After completely dissolving 1-H 19.7g (50mmol) and 11,12-dihydroindolo[2,3-a]carbazole (50mmol) in 200mL of dimethylformamide, sodium-tert-butoxide (110mmol) was added and , and stirred at 80 °C for 6 hours. The temperature was lowered to room temperature and filtered to obtain a solid, and recrystallization was performed from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 22.3 g of Compound 10 (yield 73%).

MS[M+H]+ = 611

Preparation 2-11: Synthesis of compound 11

After completely dissolving 1-I 19g (50mmol) and 11,12-dihydroindolo[2,3-a]carbazole (50mmol) in 200mL of dimethylformamide, sodium-tert-butoxide (110mmol) was added, The mixture was heated and stirred at 80° C. for 6 hours. The temperature was lowered to room temperature, filtered to obtain a solid, and recrystallized from a solution in which tetrahydrofuran and ethanol were mixed in a volume ratio of 1:3 to obtain 22.7 g of compound 11 (yield 76%).

MS[M+H]+ = 597

Various substituents were introduced through the same synthesis process as in the above reaction scheme to synthesize the materials in the embodiment.

< Experimental example 1>

< comparative example 1-1>

triplet value of 2.4 eV The host material (m-CBP) and ΔE _ST (difference between singlet energy and triplet energy) are less than 0.2 eV (delayed fluorescence) of compound 4CzIPN in the light emitting layer to prepare a green organic light emitting device, properties were evaluated.

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator. Each thin film was laminated on the prepared ITO transparent electrode by vacuum deposition at a vacuum degree of 5.0Х10 ^{-4 Pa.} First, hexaazatriphenylene-hexanitrile (HAT-CN) was thermally vacuum deposited to a thickness of 500 Å on ITO to form a hole injection layer.

The following compound NPB was vacuum-deposited on the hole injection layer to form a hole transport layer (300 Å).

On the hole transport layer, the following compound EB1 was vacuum deposited to a thickness of 100 Å to form an electron blocking layer (100 Å).

Then, the following compound m-CBP and 4CzIPN were vacuum-deposited in a weight ratio of 70:30 to a thickness of 300 Å on the electron blocking layer to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing the following compound HB1 to a thickness of 100 Å on the light emitting layer.

On the hole blocking layer, the following compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum-deposited at a weight ratio of 1:1 to form a layer for simultaneously injecting and transporting electrons to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 2,000 Å on the layer for simultaneously injecting and transporting electrons.

In the above process, the deposition rate of the organic material was maintained at 0.4 Å/sec to 0.7 Å/sec, the deposition rate of lithium fluoride of the negative electrode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was 2 x10 ^{- 7} torr to 5x10 ^{- 6} torr was maintained, an organic light emitting device was manufactured.

< Example 1-1 to 1-11>

An organic light emitting diode was manufactured in the same manner as in Comparative Example 1-1, except that the compound of Table 1 was used instead of the compound 4CzIPN in Comparative Example 1-1.

< comparative example 1-2 to 1-4>

An organic light emitting diode was manufactured in the same manner as in Comparative Example 1-1, except that compounds of the following T1 to T3 were used instead of the compound 4CzIPN in Comparative Example 1-1.

Driving voltage (V) and current efficiency (cd/A), 3000 cd measured at a current density of 10 mA/cm 2 for the organic light emitting devices of Experimental Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-4 / m and at a luminance of the ^second brightness in the CIE color coordinate and 3000cd / m ² measured at the time (T ₉₅₎ until a reduction by 95%, shown in Table 1 below.

division compound
(light emitting layer) Voltage
(V) efficiency
(cd/A) CIE color coordinates
(x,y) T ₉₅
(hr) Example 1-1 One 4.1 20 (0.21, 0.66) 93 Example 1-2 2 4.2 19 (0.20, 0.67) 91 Examples 1-3 3 4.2 20 (0.21, 0.67) 92 Examples 1-4 4 4.1 21 (0.20, 0.66) 90 Examples 1-5 5 4.2 21 (0.20, 0.66) 93 Examples 1-6 6 4.1 20 (0.21, 0.66) 95 Examples 1-7 7 4.1 19 (0.20, 0.67) 91 Examples 1-8 8 4.2 21 (0.21, 0.66) 93 Examples 1-9 9 4.2 20 (0.21, 0.67) 91 Examples 1-10 10 4.1 21 (0.20, 0.67) 94 Examples 1-11 11 4.1 21 (0.21, 0.66) 92 Comparative Example 1-1 4CzIPN 4.7 15 (0.21, 0.61) 53 Comparative Example 1-2 T1 4.9 One (0.16, 0.36) One Comparative Example 1-3 T2 4.7 6 (0.15, 0.47) 3 Comparative Example 1-4 T3 4.6 13 (0.21, 0.62) 37

As shown in Table 1, the devices of Examples 1-1 to 1-11 using the heterocyclic compound of the present invention had higher voltage than the devices of Comparative Example 1-1 using the compound 4CzIPN to which the indolocarbazolyl group was not bonded. lowered, and the efficiency improved.

In addition, when comparing the devices of Examples 1-1 to 1-11 and Comparative Examples 1-2 to 1-4, the device using the heterocyclic compound of the present invention is a compound to which a cyano group or an indolocarbazolyl group is not bonded. It can be seen that all characteristics are improved in terms of voltage, efficiency, and color purity compared to the devices of Comparative Examples 1-2 to 1-4 using

As shown in Table 1, it can be confirmed that the heterocyclic compound according to the present invention has excellent light emitting ability and high color purity, so that it can be applied to delayed fluorescence organic light emitting devices.

< Experimental example 2>

< comparative example 2-1>

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator. Each thin film was laminated on the prepared ITO transparent electrode by vacuum deposition at a vacuum degree of 5.0Х10 ^{-4 Pa.} First, hexaazatriphenylene-hexanitrile (HAT-CN) was thermally vacuum deposited to a thickness of 500 Å on ITO to form a hole injection layer.

The following compound NPB was vacuum-deposited on the hole injection layer to form a hole transport layer (300 Å).

On the hole transport layer, the following compound EB1 was vacuum deposited to a thickness of 100 Å to form an electron blocking layer (100 Å).

Then, the following compounds m-CBP, 4CzIPN and GD1 were vacuum-deposited in a weight ratio of 68:30:2 to a thickness of 300 Å on the electron blocking layer to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing the following compound HB1 to a thickness of 100 Å on the light emitting layer.

On the hole blocking layer, the following compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum-deposited at a weight ratio of 1:1 to form a layer for simultaneously injecting and transporting electrons to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 2,000 Å on the layer for simultaneously injecting and transporting electrons.

In the above process, the deposition rate of the organic material was maintained at 0.4 Å/sec to 0.7 Å/sec, the deposition rate of lithium fluoride of the negative electrode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was 2 x10 ^{- 7} torr to 5x10 ^{- 6} torr was maintained, an organic light emitting device was manufactured.

< Example 2-1 to 2-11>

An organic light emitting diode was manufactured in the same manner as in Comparative Example 2-1, except that the compound of Table 2 was used instead of the compound 4CzIPN in Comparative Example 2-1.

< comparative example 2-2 to 2-4>

An organic light emitting diode was manufactured in the same manner as in Comparative Example 2-1, except that the compound of Table 2 was used instead of the compound 4CzIPN in Comparative Example 2-1.

Driving voltage (V) and current efficiency (cd/A), 3000 cd measured at a current density of 10 mA/cm 2 for the organic light emitting devices of Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-4 CIE color coordinates measured at a luminance of /m ² were measured, and are shown in Table 2 below.

division compound
(light emitting layer) Voltage
(V) efficiency
(cd/A) CIE color coordinates
(x,y) Experimental Example 2-1 One 4.1 22 (0.18, 0.68) Experimental Example 2-2 2 4.0 22 (0.19, 0.68) Experimental Example 2-3 3 4.1 23 (0.19, 0.67) Experimental Example 2-4 4 4.1 21 (0.18, 0.67) Experimental Example 2-5 5 4.0 22 (0.19, 0.67) Experimental Example 2-6 6 4.0 21 (0.18, 0.68) Experimental Example 2-7 7 4.1 21 (0.18, 0.68) Experimental Example 2-8 8 4.0 23 (0.18, 0.67) Experimental Example 2-9 9 4.1 21 (0.19, 0.68) Experimental Example 2-10 10 4.1 22 (0.18, 0.67) Experimental Example 2-11 11 4.1 21 (0.18, 0.68) Comparative Example 2-1 4CzIPN 4.6 16 (0.16, 0.67) Comparative Example 2-2 T1 4.8 2 (0.14, 0.56) Comparative Example 2-3 T2 4.7 4 (0.16, 0.60) Comparative Example 2-4 T3 4.5 15 (0.18, 0.64)

As shown in Table 2, the devices of Examples 2-1 to 2-11 using the compound having the heterocyclic compound of the present invention as the core were Comparative Example 2-1 using the compound 4CzIPN to which the indolocarbazolyl group is not bonded. The voltage was lower than that of the device, and the efficiency was improved.

In addition, when comparing the devices of Examples 2-1 to 2-11 and Comparative Examples 2-2 to 2-4, the device using the heterocyclic compound of the present invention uses a compound to which a cyano group or an indolocarbazolyl group is not bonded. It can be seen that all of the characteristics in terms of voltage and efficiency are improved compared to the devices of Comparative Examples 2-2 to 2-4.

As shown in Table 2 above, it can be confirmed that the heterocyclic compound according to the present invention has excellent light emitting ability and can tune the light emission wavelength, so that it is possible to realize an organic light emitting device of high color purity.

< Experimental example 3>

The HOMO and LUMO energy levels were confirmed by dissolving the measured compound in dimethylformamide (dimethylformamide, DMF) at a concentration of 5 mM and electrolyte at a concentration of 0.1 M, and checking the oxidation and reduction potentials by measuring the CV device and comparing them with the ferrocene compound. .

Measurement of HOMO energy levels

The HOMO energy level of the compound and the LUMO energy level are cyclic voltages comparing the oxidation and reduction potentials of the dimethylformamide (DMF) solution in which the measurement compound is at a concentration of 5 mM and the electrolyte is dissolved at a concentration of 0.1 M, based on the ferrocene compound. It was measured by cyclic voltammetry (CV). Specific measurement conditions are as follows.

CV instrument: Iviumstat by Ivium Tech

Measurement solution: Dimethylformamide (DMF) solution in which the measurement compound is dissolved at a concentration of 5 mM and the electrolyte (KNO ₃ , Aldrich) is dissolved at a concentration of 0.1 M

Working Electrode: Carbon Electrode

Reference Electrode: Al/AgCl electrode

Counter Electrode: Platinum Electrode

Measuring temperature: 25℃

Scan rate: 50mV/S

The HOMO energy level (E(HOMO)) and the LUMO energy level (E(LUMO)) were calculated through the following equations.

E(HOMO)=[V _solvent -(E _{onset ox} -E _1/2 (solvent))]eV

E(LUMO)=[V _solvent -(E _{onset red} -E _1/2 (solvent))]eV

In the above formula, V _solvent is the energy level of the solvent, E _1/2 (solvent) is the half-wave level of the solvent, E _{onset ox} is a point where oxidation starts, and E _{onset red} is a point where reduction starts.

triplet energy measurement

The triplet energy (T1) was measured in a cryogenic state using the characteristics of a long-lived triplet exciton. Specifically, the compound is dissolved in a toluene solvent ^{to prepare a sample having a concentration of 10 -5} M, the sample is put in a quartz kit, cooled to 77K, and a 300 nm light source is irradiated to the sample for phosphorescence measurement to phosphorescence while changing the wavelength. Measure the spectrum. For the measurement of the spectrum, a spectrophotometer (FP-8600 spectrophotometer, JASCO) was used.

The vertical axis of the phosphorescence spectrum was the phosphorescence intensity, and the horizontal axis was the wavelength. A tangent line was drawn with respect to the rise of the short wavelength side of the phosphorescence spectrum, the wavelength value (λ _edge1 (nm)) of the intersection of the tangent line and the horizontal axis was obtained, and then this wavelength value was substituted into the following conversion formula 1 to calculate the triplet energy .

Conversion formula 1: T1(eV) = 1239.85/λ _edge1

The tangent to the rise of the short wavelength side of the phosphorescence spectrum is drawn as follows. First, among the maximum values of the spectrum, the maximum on the shortest wavelength side is checked. At this time, the local maximum having a peak intensity of 15% or less of the maximum peak intensity of the spectrum is not included in the maximum value on the shortest wavelength side described above. A tangent line at each point on the spectrum curve from the short wavelength side of the phosphorescence spectrum to the local maximum is considered. Among these tangents, a tangent with the largest inclination value (that is, a tangent at an inflection point) is defined as a tangent to the rise on the short-wavelength side of the phosphorescence spectrum.

single port energy measurement

The singlet energy (S1) was measured by the following method.

^{A 10 -5} M toluene solution of the compound to be measured was prepared, placed in a quartz cell, and the emission spectrum (vertical axis: luminescence intensity, horizontal axis: wavelength) of a 300 nm light source of the sample was measured at room temperature (300 K). A tangent line was drawn with respect to the rise of the short wavelength side of this emission spectrum, and the wavelength value (λ _edge2 (nm)) of the intersection of the tangent line and the horizontal axis was substituted into the following conversion equation 2 to calculate the singlet energy. The emission spectrum was measured using a spectrophotometer (FP-8600 spectrophotometer) manufactured by JASCO.

Conversion formula 2: S1(eV) = 1239.85/λ _edge2

The tangent to the rise of the short wavelength side of the emission spectrum is drawn as follows. First, among the maximum values of the spectrum, the maximum on the shortest wavelength side is checked. A tangent line at each point on the spectrum curve from the short wavelength side of the emission spectrum to the maximum is considered. Among these tangents, the tangent with the largest inclination value (that is, the tangent at the inflection point) is defined as the tangent to the rise of the short wavelength side of the emission spectrum. A maximum point having a peak intensity of 15% or less of the maximum peak intensity of the spectrum is not included in the maximum value on the shortest wavelength side described above.

The measured values of the compounds used in Examples and Comparative Examples are shown in Table 3 below.

compound S1 (eV) T1 (eV) HOMO (eV) LUMO (eV) ΔE _ST (eV) One 2.40 2.36 5.69 3.01 0.04 2 2.42 2.38 5.68 3.00 0.04 3 2.41 2.36 5.69 3.02 0.05 4 2.41 2.38 5.70 3.04 0.03 5 2.42 2.37 5.70 3.02 0.05 6 2.40 2.37 5.69 3.01 0.03 7 2.41 2.36 5.69 3.01 0.05 8 2.40 2.37 5.68 3.00 0.03 9 2.42 2.36 5.69 3.03 0.06 10 2.41 2.37 5.70 3.02 0.04 11 2.40 2.36 5.69 3.01 0.04 T1 2.99 2.26 5.45 2.63 0.73 T2 2.68 2.39 5.63 2.81 0.29 T3 2.46 2.37 5.70 3.01 0.09 4CzIPN 2.44 2.39 5.55 3.15 0.05

It can be seen that compounds 1 to 11 used in Examples of the present application are suitable as delayed fluorescent materials with ΔE _{ST of 0.3 eV or less.}

Compounds T2, T3 and 4CzIPN used as comparative examples _{correspond to delayed fluorescent materials with ΔE ST} of 0.3 eV or less, but as shown in Tables 1 and 2, the heterocyclic compounds of the present invention (Compounds 1 to 11) It can be seen that the devices of Examples (Examples 1-1 to 1-11 and 2-1 to 2-11) using can

Although preferred experimental examples of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and detailed description of the invention, and this also falls within the scope of the invention. .

1: substrate
2: Anode
3: organic layer
4: cathode
5: hole injection layer
6: hole transport layer
7: Electronic blocking layer
8: light emitting layer
9: hole blocking layer
10: electron transport layer
11: electron injection layer
12: A layer that simultaneously injects and transports electrons

Claims (10)

A heterocyclic compound represented by the following formula (1):
[Formula 1]

In Formula 1,
S1 to S5, S11 to S15, S1' to S5' and S11' to S15' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
a5 is an integer from 0 to 3,
HAr1 is a group represented by the following formula (A),
[Formula A]

In the formula A,
Two of X1 to X3 are N, and the other is N or CR,
R, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
HAr2 is a group represented by the following formula (B),
[Formula B]

In Formula B,
G is hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
b is an integer from 0 to 8, and when b is 2 or more, G is the same as or different from each other,
a1 is 0 or 1,
a2 to a4 are each independently an integer of 0 to 3,
When a3 is 2 or more, HAr1 are the same as or different from each other,
When a4 is 2 or more, HAr2 is the same as or different from each other. The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 1-1 or 1-2:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
S1 to S5, S11 to S15, S1' to S5', S11' to S15', HAr1, HAr2, and a1 to a5 are the same as defined in Formula 1. The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by any one of the following Chemical Formulas 2-1 to 2-3:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,
R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; HAr1; or HAr2,
At least one of R1 to R4 is a cyano group,
At least one of R5 and R6 is a cyano group,
At least one of R7 and R8 is a cyano group,
The definitions of S1 to S5, S11 to S15, S1' to S5', S11' to S15', HAr1 and HAr2 are as defined in Formula 1,
When HAr1 is 2 or more, HAr1 is the same as or different from each other,
When HAr2 is 2 or more, HAr2 is the same as or different from each other. The heterocyclic compound of claim 1, wherein the heterocyclic compound contains at least one deuterium. The heterocyclic compound according to claim 1, wherein the heterocyclic compound is any one selected from the following compounds:

. _{The heterocyclic compound according to claim 1, wherein the difference (ΔE ST} ) between the singlet energy (S1) and the triplet energy (T1) of the heterocyclic compound represented by Formula 1 is 0 eV or more and 0.3 eV or less. anode; cathode; and an organic material layer provided between the anode and the cathode, wherein the organic material layer includes the heterocyclic compound according to any one of claims 1 to 6. The organic light-emitting device of claim 7 , wherein the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound. The method according to claim 7, wherein the organic material layer is an electron injection layer; electron transport layer; a layer that simultaneously injects and transports electrons; or a hole blocking layer, the electron injection layer; electron transport layer; a layer that simultaneously injects and transports electrons; Or the hole blocking layer is an organic light emitting device comprising the heterocyclic compound. The method according to claim 7, wherein the organic material layer is a hole injection layer; hole transport layer; a layer that simultaneously injects and transports holes; Or including an electron blocking layer, the hole injection layer; hole transport layer; a layer that simultaneously injects and transports holes; Or the electron blocking layer is an organic light emitting device comprising the heterocyclic compound.

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