阅读说明：本技术 含氘化合物和包含其的有机发光器件 (Deuterium-containing compound and organic light-emitting device comprising same ) 是由 尹洪植 洪玩杓 金振珠 李东勋 金明坤 于 2019-10-25 设计创作，主要内容包括：本说明书提供了由式1表示的化合物和包含其的有机发光器件。(The present specification provides a compound represented by formula 1 and an organic light emitting device including the same.)

1. A compound represented by the following formula 1:

[ formula 1]

In the formula 1, the first and second groups,

x1 to X6 are the same or different from each other and are each independently N, C (A1), C (A2), C (A3), C (A4), C-H, C-D or C-R ', and R' is aryl,

provided that (1) three of X1-X6 are C-D, one of which is C (A2), one of which is C (A4), and one of which is N, C (A2), C (A4), C-H, C-D or C-R', or (2) at least one of X1-X6 is C (A1) or C (A2), at least one of which is C (A3) or C (A4), and at least one of X1-X6 is C (A1) or C (A3),

a1 is any one of the following a-1 to a-4, and when two or more A1 are present, A1 are the same as or different from each other,

in a-1 to a-3, a1 is an integer of 1 to 4, a2 is an integer of 1 to 8, and a3 is an integer of 1 to 8,

a2 is the following b-1 or b-2, and when two or more A2 are present, A2 are the same as or different from each other,

a3 is c-1 or c-2 below, and when two or more A3 are present, A3 are the same as or different from each other,

a4 is d-1 or d-2 below, and when two or more A4 are present, A4 are the same as or different from each other,

in b-1, b-2, c-1 and d-1,

r1 to R8 are the same as or different from each other, and each is independently any one group selected from the group consisting of: hydrogen; an alkyl group; an aryl group; and heteroaryl, or a group in which two or more groups selected from the group are linked,

b1 is an integer of 0 to 8, and when b1 is 2 or more, R1 are the same as or different from each other,

b2 is an integer of 0 to 4, and when b2 is 2 or more, R2 are the same as or different from each other,

b3 is an integer of 0 to 2, and when b3 is 2, R3 are the same as or different from each other, an

b4 is an integer of 0 to 4, and when b4 is 2 or more, R4 are the same as or different from each other.

2. The compound according to claim 1, wherein formula 1 is represented by the following formula 1-1 or 1-2:

[ formula 1-1]

In the formula 1-1, the compound represented by the formula,

x is N or CR26, and R26 is A1, A2, A3, A4, H, D or aryl,

at least one of R21-R25 is A1 or A2, at least one of which is A3 or A4, and at least one of R21-R25 is A1 or A3,

[ formulae 1-2]

In the formula 1-2, the compound represented by the formula,

r27 is A2, R28 is A4, and R29 is A2, A4, H, D or aryl, and

in formulas 1-1 and 1-2, the definitions of A1, A2, A3 and A4 are the same as those defined in formula 1.

3. The compound of claim 2, wherein formulae 1-2 are represented by formula 2 below:

[ formula 2]

In formula 2, the definitions of R27 to R29 are the same as those defined in formula 1-2.

4. The compound of claim 1, wherein a-1 is any one of the following a-11 to a-15:

5. the compound of claim 1, wherein a-2 is the following a-21 or a-22:

6. the compound of claim 1, wherein a-3 is any one of the following a-31 to a-33:

7. the compound according to claim 1, wherein the compound represented by formula 1 is any one selected from the group consisting of:

8. the compound of claim 1, wherein the singlet energy level of the compound represented by formula 1 (S1)_D) And the triplet energy level of the compound represented by formula 1 (T1)_D) Difference of difference (DeltaST)_D) Is 0eV to 0.3 eV.

9. An organic light emitting device comprising:

a first electrode;

a second electrode disposed to face the first electrode; and

a light emitting layer disposed between the first electrode and the second electrode,

wherein the light-emitting layer comprises a compound according to any one of claims 1 to 8.

10. The organic light-emitting device of claim 9, wherein the light-emitting layer further comprises a host, and the triplet energy level (T1) of the host_H) Higher than the triplet energy level (T1) of the compound represented by formula 1_D)。

11. The organic light-emitting device according to claim 9, wherein the light-emitting layer further comprises a host, and a singlet energy level of the host (S1)_H) Is higher than the singlet energy level of the compound represented by formula 1 (S1)_D)。

Technical Field

The present invention relates to a deuterium containing compound and an organic light emitting device comprising the same.

This application claims priority and benefit to korean patent application No. 10-2018-0128593, filed on 26.10.2018 from the korean intellectual property office, the entire contents of which are incorporated herein by reference.

Background

The present invention relates to a novel organic compound which can be advantageously used for an organic light-emitting device. More particularly, the present invention relates to Thermally Activated Delayed Fluorescence (TADF) materials substituted with deuterium and their use for OLEDs.

The fluorescent light-emitting material utilizing the phenomenon of thermally activated delayed fluorescence is also referred to as thermally activated delayed fluorescence (thermally activated delayed fluorescence, hereinafter, appropriately abbreviated as "TADF") utilizing the phenomenon in which reverse intersystem crossing (hereinafter, appropriately abbreviated as "RISC") from triplet excitons to singlet excitons occurs, and its applicability for organic EL devices has been reported. When delayed fluorescence is used by the TADF mechanism, even in fluorescence emission excited by an electric field, an internal quantum efficiency equivalent to 100% of phosphorescence emission is theoretically possible.

In order to exhibit the TADF phenomenon, reverse intersystem crossing from 75% of triplet excitons to singlet excitons, which is generated by excitation of an excitation electric field at room temperature or the temperature of a light emitting layer in a light emitting device, needs to occur. Furthermore, singlet excitons generated by reverse intersystem crossing emit fluorescence similar to 25% singlet excitons generated by direct excitation, making internal quantum efficiency of 100% theoretically possible. In order for reverse intersystem crossing to occur, the difference (Δ ST) between the singlet level (S1) and the triplet level (T1) needs to be small.

For example, in order to exhibit the TADF phenomenon, it is effective to reduce Δ ST of an organic compound, and in order to reduce Δ ST, it is advantageous to clearly separate the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) in a molecule without mixing the HOMO and LUMO.

However, when the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) in a molecule are clearly separated without mixing the HOMO and LUMO, the pi-conjugated system in the molecule is reduced or cut off, and thus it is difficult to make the reverse intersystem crossing compatible with stability, and therefore, the lifetime of the light-emitting device is shortened.

Therefore, new methods for increasing TADF lifetime are needed.

Disclosure of Invention

Technical problem

The present invention is directed to provide a compound and an organic light emitting device including the same: it has a small singlet energy level (S1)_D) And triplet energy level (T1)_D) Difference of difference (Δ ST)_D) And thus has the high efficiency and good lifetime characteristics of organic light emitting devices when included in the light emitting layer of the device.

Technical scheme

An exemplary embodiment of the present specification provides a compound represented by the following formula 1.

[ formula 1]

In the formula 1, the first and second groups,

x1 to X6 are the same or different from each other and are each independently N, C (A1), C (A2), C (A3), C (A4), C-H, C-D or C-R ', and R' is aryl,

provided that (1) three of X1-X6 are C-D, one of which is C (A2), one of which is C (A4), and one of which is N, C (A2), C (A4), C-H, C-D or C-R', or (2) at least one of X1-X6 is C (A1) or C (A2), at least one of which is C (A3) or C (A4), and at least one of X1-X6 is C (A1) or C (A3),

a1 is any one of the following a-1 to a-4, and when two or more A1 are present, A1 are the same as or different from each other,

in a-1 to a-3, a1 is an integer of 1 to 4, a2 is an integer of 1 to 8, and a3 is an integer of 1 to 8,

a2 is the following b-1 or b-2, and when two or more A2 are present, A2 are the same as or different from each other,

a3 is c-1 or c-2 below, and when two or more A3 are present, A3 are the same as or different from each other,

a4 is d-1 or d-2 below, and when two or more A4 are present, A4 are the same as or different from each other,

in b-1, b-2, c-1 and d-1,

r1 to R8 are the same as or different from each other, and each is independently any one group selected from the group consisting of: hydrogen; an alkyl group; an aryl group; and heteroaryl, or a group in which two or more groups selected from the group are linked,

b1 is an integer of 0 to 8, and when b1 is 2 or more, R1 are the same as or different from each other,

b2 is an integer of 0 to 4, and when b2 is 2 or more, R2 are the same as or different from each other,

b3 is an integer of 0 to 2, and when b3 is 2, R3 are the same as or different from each other, an

b4 is an integer of 0 to 4, and when b4 is 2 or more, R4 are the same as or different from each other.

Further, an exemplary embodiment of the present specification provides an organic light emitting device including: a first electrode; a second electrode disposed to face the first electrode; and a light-emitting layer disposed between the first electrode and the second electrode, wherein the light-emitting layer includes a compound represented by formula 1.

Advantageous effects

In some exemplary embodiments, an organic light emitting device including the compound of the present invention has high efficiency or excellent life span characteristics.

In one exemplary embodiment, the compound represented by formula 1 may be used in a light emitting layer of an organic light emitting device.

Drawings

Fig. 1 shows an example of an organic light-emitting device composed of a substrate 1, a positive electrode 2, a light-emitting layer 8, and a negative electrode 4.

Fig. 2 shows an example of an organic light-emitting device composed of a substrate 1, a positive electrode 2, a hole injection layer 5, a hole transport layer 6, a hole adjusting layer 7, a light-emitting layer 8, an electron transport layer 9, an electron injection layer 10, and a negative electrode 4.

[ description of reference numerals ]

1: substrate

2: positive electrode

3: organic material layer

4: negative electrode

5: hole injection layer

6: hole transport layer

7: hole-regulating layer

8: luminescent layer

9: electron transport layer

10: electron injection layer

Detailed Description

Hereinafter, the present invention will be described in more detail.

In the context of the present specification,means a moiety bonded to another substituent or bonding moiety.

In an exemplary embodiment, the term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent. The position at which the substituent is substituted is not limited as long as the position is a position at which a hydrogen atom is substituted (i.e., a position at which the substituent can be substituted). When two or more substituents are present, the two or more substituents may be the same as or different from each other.

In the present specification, "energy level" means the magnitude of energy. Therefore, even when the energy level is expressed in the negative (-) direction from the vacuum level, it is interpreted that the energy level means an absolute value of the corresponding energy value. For example, a large energy level means that the absolute value increases in a negative direction from the vacuum level. In the present specification, the expression that the energy level is "deep" or "high" has the same meaning as the expression that the energy level is large.

In the present specification, the triplet level may be measured by using a spectroscopic instrument capable of measuring fluorescence and phosphorescence. Specifically, the triplet energy level may be determined by: using toluene or Tetrahydrofuran (THF) as solvent at very low temperature using liquid nitrogen at 10 deg.C^-6Concentration of M a solution is prepared, the solution is irradiated with a light source of an absorption wavelength band of the material, then luminescence at a singlet level is excluded from a light emission spectrum, and a spectrum emitted at a triplet level is analyzed. When electrons are excited from a light source, the two components can be separated from each other in an extremely low temperature state because the time for which the electrons stay at the triplet energy level is much longer than the time for which the electrons stay at the singlet energy level. In the present specification, the singlet level is measured by using a fluorescence instrument, and unlike the above-described method for measuring the triplet level, the singlet level may be measured by irradiating a solution with a light source at room temperature.

In this specification, unless specifically described otherwise, when a portion "includes" one constituent element, this does not mean that another constituent element is excluded, but means that another constituent element may also be included.

In this specification, when one member is disposed "on" another member, this includes not only a case where one member is in contact with another member but also a case where another member is present between the two members.

Examples of the substituent in the present specification will be described below, but are not limited thereto.

In the present specification, alkyl means a straight-chain or branched saturated hydrocarbon. The number of carbon atoms of the alkyl group is not particularly limited, but is 1 to 40; 1 to 20; 1 to 10; or 1 to 6. The alkyl group may be linear or cyclic.

Specific examples of the chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methylpentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethylpropyl, 1-dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

The number of carbon atoms of the cyclic alkyl (cycloalkyl) group is not particularly limited, but is 3 to 40; 3 to 24; 3 to 14; or 3 to 8. Specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.

In the present specification, aryl means a substituted or unsubstituted monocyclic or polycyclic ring which is fully or partially unsaturated. The number of carbon atoms thereof is not particularly limited but is 6 to 60; 6 to 40; or 6 to 30. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. Examples of monocyclic aryl groups include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto. Examples of polycyclic aromatic groups include naphthyl, anthracenyl, phenanthrenyl, perylenyl, fluoranthenyl, triphenylenyl, phenalkenyl, pyrenyl, tetracenyl, perylene,A phenyl group, a pentacenyl group, a fluorenyl group, an indenyl group, an acenaphthenyl group, a benzofluorenyl group, a spirofluorenyl group, and the like, but is not limited thereto.

In the present specification, when it is said that the fluorenyl group may be substituted, the substituted fluorenyl group includes all compounds in which substituents of a pentagonal ring of the fluorenyl group are spiro-bonded to each other to form an aromatic hydrocarbon. Examples of substituted fluorenes include, but are not limited to, 9 '-spirobifluorene, spiro [ cyclopentane-1, 9' -fluorene ], spiro [ benzo [ c ] fluorene-7, 9-fluorene ], and the like.

In the present specification, the heteroaryl group is a cyclic group containing one or more of N, O and S as a heteroatom, and the number of carbon atoms thereof is not particularly limited but is 2 to 40; 2 to 30; or 2 to 20. Examples of heteroaryl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,Azolyl group,Oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, carbolinyl, acenaphthoquinoxalinyl, indenoquinazolinyl, indenoisoquinolinyl, indenoquinolinyl, pyridoindolyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, quinoxalinyl, pyridopyrazinyl, pyrazinyl, quinoxalinyl, indolyl, carbazolyl, and the likeAzolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl, thiazolyl, isoquinoylAzolyl group,Oxadiazolyl, thiadiazolyl, benzothiazolyl, thiophenylOxazinyl, phenothiazinyl, dibenzofuranyl, and the like, but is not limited thereto. Heteroaryl includes aliphatic heteroaryl and aromatic heteroaryl.

Hereinafter, various exemplary embodiments of the present invention will be described in more detail.

An exemplary embodiment of the present specification provides a compound represented by the following formula 1.

[ formula 1]

In the formula 1, the first and second groups,

x1 to X6 are the same or different from each other and are each independently N, C (A1), C (A2), C (A3), C (A4), C-H, C-D or C-R ', and R' is aryl,

provided that (1) three of X1-X6 are C-D, one of which is C (a2), one of which is C (a4), and one of which is N, C (a2), C (a4), C-H, C-D, or C-R', or (2) at least one of X1-X6 is C (a1) or C (a2), at least one of which is C (A3) or C (a4), and at least one of X1-X6 is C (a1) or C (A3).

The compound represented by formula 1 includes both carbazole or indolocarbazole serving as an electron donor and triazine or cyano group serving as an electron acceptor. Accordingly, the compound represented by formula 1 may have delayed fluorescence characteristics because the orbital forms of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) in a molecule are separated by 50% or more.

Since the structure further including cyano group or triazine like the compound represented by formula 1 has a smaller difference between the triplet level and the singlet level than the structure including only indolocarbazole or carbazole, the delayed fluorescence characteristic by reverse intersystem crossing (RISC) is better.

In an exemplary embodiment, at least one of X1 to X6 is C (a4), and a4 is d-2. When A4 is d-2, -CN is directly bonded to the central core comprising X1. When — CN is connected to a core including X1 through an aryl group, the LUMO (lowest unoccupied molecular orbital) energy level decreases due to the expansion of conjugation, so that the difference between the triplet energy level and the singlet energy level becomes larger, and thus the delayed fluorescence characteristic decreases.

The nitrogen of carbazole or indolocarbazole contained in the compound represented by formula 1 is bonded to a ring containing X1. Therefore, the compound represented by formula 1 has a smaller difference between the singlet level and the triplet level than that of a structure in which a carbon of carbazole or indolocarbazole is bonded to a ring including X1, and thus has better delayed fluorescence characteristics.

The compound represented by formula 1 is a deuterium-containing compound containing at least one deuterium.

Most of the chemical properties do not change when some or all of the hydrogens present in the compound are replaced with deuterium. However, since the atomic weight of deuterium is twice the atomic weight of hydrogen, when hydrogen of a compound is substituted by deuterium, the vibration mode of the compound becomes small, so that the vibration level becomes low. Therefore, when hydrogen atoms present in the compound are substituted with deuterium, intermolecular van der waals force is reduced, so that it is possible to prevent quantum efficiency from being lowered due to collision caused by intermolecular vibration. Furthermore, the C-D bond improves the stability of the compound.

In one exemplary embodiment, the compound represented by formula 1 is in a form wherein any one of X1 to X6 is C-D, C (a1) or C (A3), and includes deuterium.

In an exemplary embodiment, A1 is any one of the following a-1 to a-4.

In a-1 to a-3, a1 is an integer of 1 to 4, a2 is an integer of 1 to 8, and a3 is an integer of 1 to 8.

In an exemplary embodiment, A3 is c-1 or c-2 below.

In one exemplary embodiment, the compound represented by formula 1 comprises carbazole represented by a-1, wherein 1 to 4 deuterium groups are substituted. Due to kinetic isotope effects, the reaction rate of a chemical process of a compound containing a C-D bond may be slower than that of a compound containing only a C-H bond. When the chemical decomposition of the luminescent compound is accompanied by the cleavage of the C-H bond, the stability of the compound is improved due to the stronger C-D bond.

In an exemplary embodiment, a1 is 1.

In an exemplary embodiment, a1 is 2.

In an exemplary embodiment, a1 is 4.

In an exemplary embodiment, a-1 is any one of the following a-11 to a-15.

In one exemplary embodiment, the compound of formula 1 comprises a compound represented by a-2 and substituted with-CD₃The carbazole of (1).

When the benzene ring of carbazole is substituted by-CH₃When the benzylic protons are particularly reactive, the chemical decomposition may be promoted in the luminescent compound. In this case, when-CH₃When the hydrogen in (a) is replaced by deuterium, the stability of the compound can be increased. Since the Van der Waals radius of C-D is smaller than the Van der Waals radius of C-H, -CD₃Is having a ratio-CH₃Less sterically hindered substituents. Thus, when the compound has-CD in the benzene ring of carbazole₃As a substituent, distortion on the aromatic ring is small, so that conjugation of the compound can be improved, and efficiency and lifetime of the device can be improved.

In an exemplary embodiment, a2 is 1.

In an exemplary embodiment, a2 is 2.

In an exemplary embodiment, a-2 is a-21 or a-22 below.

In an exemplary embodiment, the compound of formula 1 comprises a compound represented by a-3 and substituted with-C₆D₅The carbazole of (1).

When carbazole is substituted with phenyl group, the distribution of HOMO (highest occupied molecular orbital) can be enlarged by phenyl group, and when hydrogen of phenyl group is substituted with deuterium, C-D bond can improve stability of the compound. Thus, the efficiency and lifetime of the device may be improved.

In an exemplary embodiment, a3 is 1.

In an exemplary embodiment, a-3 is any one of the following a-31 to a-33.

In an exemplary embodiment, A2 is b-1 or b-2 below, and when two or more A2 are present, A2 are the same or different from each other,

a4 is d-1 or d-2 below, and when two or more A4 are present, A4 are the same as or different from each other,

in b-1, b-2 and d-1,

r1 to R5, R7 and R8 are the same or different from each other, and each is independently any one group selected from the group consisting of: hydrogen; an alkyl group; an aryl group; and heteroaryl, or a group in which two or more groups selected from the group are linked,

b1 is an integer of 0 to 8, and when b1 is 2 or more, R1 are the same as or different from each other,

b2 is an integer of 0 to 4, and when b2 is 2 or more, R2 are the same as or different from each other,

b3 is an integer of 0 to 2, and when b3 is 2, R3 are the same as or different from each other, an

b4 is an integer of 0 to 4, and when b4 is 2 or more, R4 are the same as or different from each other.

In an exemplary embodiment, formula 1 is represented by formula 1-1 or 1-2 below.

[ formula 1-1]

In the formula 1-1, the compound represented by the formula,

x is N or CR26, and R26 is A1, A2, A3, A4, H, D or aryl,

at least one of R21-R25 is A1 or A2, at least one of which is A3 or A4, and at least one of R21-R25 is A1 or A3,

[ formulae 1-2]

In the formula 1-2, the compound represented by the formula,

r27 is A2, R28 is A4, and R29 is A2, A4, H, D or aryl, and

in formulas 1-1 and 1-2, the definitions of A1, A2, A3 and A4 are the same as those defined in formula 1.

In an exemplary embodiment, R1 to R8 are the same or different from each other and each is independently any one group selected from the group consisting of: hydrogen; C1-C10 alkyl; a C6-C30 aryl group; and a C2-C30 heteroaryl group, or a group in which two or more groups selected from the group are linked.

In an exemplary embodiment, R1 to R8 are the same or different from each other and each is independently any one group selected from the group consisting of: hydrogen; C1-C6 alkyl; a C6-C25 aryl group; and a C2-C25 heteroaryl group, or a group in which two or more groups selected from the group are linked.

In an exemplary embodiment, R1 to R8 are the same or different from each other and each is independently any one group selected from the group consisting of: hydrogen; C1-C4 alkyl; a C6-C18 aryl group; and a C2-C18 heteroaryl group, or a group in which two or more groups selected from the group are linked.

In an exemplary embodiment, R1 to R8 are the same or different from each other and are each independently hydrogen; a methyl group; unsubstituted or alkyl-substituted aryl; or unsubstituted or aryl-substituted heteroaryl.

In an exemplary embodiment, R1 to R8 are the same or different from each other and are each independently hydrogen; a methyl group; a phenyl group; a naphthyl group; a dimethyl fluorenyl group; a dibenzofuranyl group; a dibenzothienyl group; or carbazolyl substituted with phenyl.

In an exemplary embodiment, R1 is methyl; a phenyl group; or carbazolyl substituted with phenyl.

In an exemplary embodiment, R2 to R5 are the same or different from each other and are each independently hydrogen; a phenyl group; a dimethyl fluorenyl group; a naphthyl group; a dibenzofuranyl group; or dibenzothienyl.

In an exemplary embodiment, R2 to R6 are the same or different from each other and are each independently hydrogen; a phenyl group; a dimethyl fluorenyl group; a naphthyl group; a dibenzofuranyl group; or dibenzothienyl.

In an exemplary embodiment, R6 to R8 are the same or different from each other and are each independently hydrogen; a phenyl group; a dibenzofuranyl group; a dibenzothienyl group; or carbazolyl substituted with phenyl.

In an exemplary embodiment, R5 to R8 are the same or different from each other and are each independently hydrogen; a phenyl group; a dibenzofuranyl group; a dibenzothienyl group; or carbazolyl substituted with phenyl.

In an exemplary embodiment, R' is a C6-C36 aryl group; a C6-C30 aryl group; or a C6-C25 aryl group.

In an exemplary embodiment, R' is phenyl.

In an exemplary embodiment, three of X1-X6 are C-D, one of which is C (A2), one of which is C (A4), and one of which is C (A2), C (A4), C-H, C-D, or C-R'.

In an exemplary embodiment, three of X1-X6 are C-D, one of which is C (a2), one of which is C (a4), and one of which is C (a2) or C (a 4).

In an exemplary embodiment, at least one of X1 to X6 is C (a 1).

In an exemplary embodiment, at least one of X1 to X6 is C (A3).

In an exemplary embodiment, zero or one of X1 to X6 is N.

In an exemplary embodiment, at least one of X1 to X6 is C (a4), and a4 is d-2.

In an exemplary embodiment, at least two of X1 to X6 are C (a4) and two a4 are each d-2.

In an exemplary embodiment, formulae 1-2 are represented by formula 2 below.

[ formula 2]

In formula 2, the definitions of R27 to R29 are the same as those defined in formula 1-2.

In one exemplary embodiment, the compound represented by formula 1 is any one selected from the following compounds.

In one exemplary embodiment, the compound represented by formula 1 is a fluorescent material.

In one exemplary embodiment, the compound represented by formula 1 is a delayed fluorescence material.

In one exemplary embodiment, the compound represented by formula 1 may be used as a green dopant of a light emitting layer.

An exemplary embodiment of the present specification provides an organic light emitting device including: a first electrode; a second electrode disposed to face the first electrode; and a light-emitting layer disposed between the first electrode and the second electrode, wherein the light-emitting layer comprises the compound represented by formula 1 described above.

In one exemplary embodiment, the light emitting layer may also be composed of only the compound represented by formula 1 described above, and may further include other materials than the compound represented by formula 1. In one exemplary embodiment, the compound represented by formula 1 may also be used as a host, and may also be used together with other host materials to serve as a dopant. In one exemplary embodiment, the compound represented by formula 1 may also receive holes and electrons through the host to generate excitons, and may also directly receive holes and electrons from a layer adjacent to the light emitting layer without passing through the host to generate excitons. However, the role of the compound represented by formula 1 in the light emitting layer is not limited thereto, and may contribute to improvement of the characteristics of the device in various ways depending on the combination of compounds contained in the light emitting layer.

An exemplary embodiment of the present description includes: a first electrode; a second electrode disposed to face the first electrode; and a light emitting layer disposed between the first electrode and the second electrode, the light emitting layer including a compound represented by formula 1 as a dopant and further including a host.

In one exemplary embodiment, the mechanism by which light emission may occur in the light emitting layer is not limited and may vary depending on the compound used in the light emitting layer.

In one exemplary embodiment, holes and electrons move to a compound (dopant) represented by formula 1 through a host, excitons are generated in the dopant at a ratio of 3:1 for a triplet state and a singlet state, and then the excitons generated for the triplet state of the dopant are transferred to the singlet state of the dopant to emit light, and the excitons generated for the singlet state may emit light as if they were in the singlet state. In another exemplary embodiment, a host used only as a host material is included in the light emitting layer, and holes, electrons, or holes and electrons are injected into the dopant without passing through the host, and thus, excitons may also be formed in a triplet state and a singlet state. However, this is merely an example of a light emitting mechanism, and light emission may occur by other different light emitting mechanisms.

In one exemplary embodiment, the light emitting layer includes a compound represented by formula 1 as a dopant.

In one exemplary embodiment, the emission wavelength of the compound represented by formula 1 is 500nm to 565 nm.

In an exemplary embodiment, the singlet energy level of the compound represented by formula 1 (S1)_D) And triplet energy level (T1)_D) Difference of difference (DeltaST)_D) Is 0eV to 0.3eV, preferably 0eV to 0.2 eV.

In the present specification, the singlet energy level of the compound represented by formula 1 (S1)_D) And triplet energy level (T1)_D) Difference of difference (DeltaST)_D) Meaning T1_D-S1_DAbsolute value of (a).

When the singlet energy level of the compound represented by formula 1 (S1)_D) And triplet energy level (T1)_D) Difference of difference (DeltaST)_D) When the above range is satisfied, the rate and speed at which excitons generated in a triplet state move to a singlet state due to reverse intersystem crossing (RISC) are increased, and thus the time during which the excitons stay in the triplet state is reduced, so that there is an advantage in that the efficiency and lifespan of the organic light emitting device are increased.

In an exemplary embodiment, the triplet energy level of the host (T1)_H) Is 2.4eV or more.

In an exemplary embodiment, the singlet energy level of the host (S1)_H) Is 2.1eV to 2.8 eV.

In an exemplary embodiment, the triplet energy level of the host (T1)_H) Higher than the triplet energy level (T1) of the compound represented by formula 1_D)。

In an exemplary embodiment, the singlet energy level of the host (S1)_H) Is higher than the singlet energy level of the compound represented by formula 1 (S1)_D) And when said energy relationship is satisfied, mayTo prevent excitons of the dopant from being moved back to the host in reverse.

In one exemplary embodiment, the host may be dibenzofuran; dibenzofuran derivatives; dibenzothiophene; or a dibenzothiophene derivative.

In an exemplary embodiment, the host is at least one selected from the following structures.

In one exemplary embodiment, the light emitting layer including the compound represented by formula 1 may further include a fluorescent light emitting type material.

When the light emitting layer further includes a fluorescent light emitting material, excitons move from the compound represented by formula 1 to the fluorescent light emitting material to finally emit light in the fluorescent light emitting type material, so that the color purity of the device can be increased by using the fluorescent light emitting type material having a narrow full width at half maximum, and the lifespan of the device can be increased by preventing exciton-polaron quenching of the compound represented by formula 1.

In an exemplary embodiment, the light emitting layer may further include other fluorescent light emitting type materials.

In one exemplary embodiment, the fluorescent light emitting type material may be a fluorene derivative; a naphthalene derivative; an anthracene derivative; a tetracene derivative; a pyrene derivative;a derivative; a fluoranthene derivative; a perylene derivative; quinolino [2,3-b]Acridine-7, 14(5H,12H) -dione derivatives; 4H-chromene derivatives; 1,2,3,5,6, 7-hexahydroPyrido [3,2,1-ij]A quinoline derivative; benzo- α -pyrone (═ coumarin) derivatives; 4H pyran derivatives; benzo [ d ] carbonyl]A thiazole derivative; a pyrrole derivative; a quinazol derivative; a carbazole derivative; 2,3,6, 7-tetrahydro-1H-pyrano [2,3-f ]]Pyrido [3,2,1-ij]Quinolin-11 (5H) -one derivatives; boron-based derivatives, and the like, but are not limited thereto.

In one exemplary embodiment, the organic light emitting device includes a phosphorescent emission type light emitting layer in addition to the light emitting layer including the compound represented by formula 1.

In one exemplary embodiment, the organic light emitting device includes a plurality of light emitting layers, and the light emitting layers are formed adjacent to each other.

In the present specification, the case where any organic material layer contains any compound means that one or more compounds are contained.

In one exemplary embodiment, when one or more compounds represented by formula 1 are included in the light emitting layer, the weight part of the compound represented by formula 1 means the sum of the weight parts of the one or more compounds represented by formula 1.

In one exemplary embodiment, the organic light emitting device further includes one or more organic material layers.

In one exemplary embodiment, the organic light emitting device further includes one or more organic material layers between the first electrode and the light emitting layer.

In one exemplary embodiment, the organic light emitting device further includes one or more organic material layers between the second electrode and the light emitting layer.

In one exemplary embodiment, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a layer simultaneously transporting and injecting holes, a hole adjusting layer, a light emitting layer, an electron adjusting layer, an electron transport layer, an electron injection layer, a layer simultaneously transporting and injecting electrons, and the like as an organic material layer.

In another exemplary embodiment, the organic light emitting device may be a normal type organic light emitting device in which a positive electrode, one or more organic material layers, and a negative electrode are sequentially stacked on a substrate.

In one exemplary embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a negative electrode, one or more organic material layers, and a positive electrode are sequentially stacked on a substrate.

In one exemplary embodiment, the first electrode is a positive electrode and the second electrode is a negative electrode.

In another exemplary embodiment, the first electrode is a negative electrode and the second electrode is a positive electrode.

A structure of an organic light emitting device according to an exemplary embodiment of the present specification is illustrated in fig. 1 and 2.

As shown in fig. 1, an organic light emitting device according to an exemplary embodiment of the present invention may be composed of a substrate 1, a positive electrode 2, a light emitting layer 8, and a negative electrode 4. In one exemplary embodiment, the compound represented by formula 1 is contained in the light emitting layer 8.

As shown in fig. 2, the organic light emitting device according to an exemplary embodiment of the present invention may be composed of a substrate 1, a positive electrode 2, a hole injection layer 5, a hole transport layer 6, a hole adjusting layer 7, a light emitting layer 8, an electron transport layer 9, an electron injection layer 10, and a negative electrode 4. In one exemplary embodiment, the compound represented by formula 1 is contained in the light emitting layer 8.

However, the structure of the organic light emitting device according to one exemplary embodiment of the present specification is not limited to those of fig. 1 and 2, and may be any of the following structures.

(1) Positive electrode/hole transport layer/light emitting layer/negative electrode

(2) Positive electrode/hole injection layer/hole transport layer/light emitting layer/negative electrode

(3) Positive electrode/hole transport layer/light-emitting layer/electron transport layer/negative electrode

(4) Positive electrode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/negative electrode

(5) Positive electrode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/negative electrode

(6) Positive electrode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/negative electrode

(7) Positive electrode/hole transport layer/hole regulating layer/light emitting layer/electron transport layer/negative electrode

(8) Positive electrode/hole transport layer/hole control layer/light-emitting layer/electron transport layer/electron injection layer/negative electrode

(9) Positive electrode/hole injection layer/hole transport layer/hole regulation layer/light-emitting layer/electron transport layer/negative electrode

(10) Positive electrode/hole transport layer/light-emitting layer/electron regulating layer/electron transport layer/negative electrode

(11) Positive electrode/hole transport layer/light-emitting layer/electron control layer/electron transport layer/electron injection layer/negative electrode

(12) Positive electrode/hole injection layer/hole transport layer/light-emitting layer/electron modulating layer/electron transport layer/negative electrode

(13) Positive electrode/hole injection layer/hole transport layer/light-emitting layer/electron modulating layer/electron transport layer/electron injection layer/negative electrode

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 a first electrode, an organic material layer, and a second electrode on a substrate. In this case, the organic light emitting device may be manufactured by: a metal, or a metal oxide having conductivity, or an alloy thereof is deposited on a substrate by using a Physical Vapor Deposition (PVD) method such as sputtering or electron beam evaporation to form a positive electrode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the positive electrode, and then a material that can be used as a negative electrode is deposited on the organic material layer.

In addition, in manufacturing an organic light emitting device, the compound represented by formula 1 may be formed into an organic material layer not only by a vacuum deposition method but also by a solution application method. Here, the solution application method means spin coating, dip coating, blade coating, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

In addition to the method as described above, the organic light emitting device may be manufactured by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate. However, the manufacturing method is not limited thereto.

As the positive electrode material, a material having a high work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO: Al or SnO₂Sb; conducting polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole and polyaniline; and the like, but are not limited thereto.

As the negative electrode material, a material having a low work function is generally preferred 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; materials of multilayer construction, e.g. LiF/Al or LiO₂Al; and the like, but are not limited thereto.

The hole injection layer is a layer that injects holes received from the electrode into the light-emitting layer or an adjacent layer disposed on the side of the light-emitting layer. As the hole injection material, a compound of: it has an ability to transport holes, and thus has an effect of injecting holes at a positive electrode and an excellent hole injection effect for a light emitting layer or a light emitting material, prevents excitons generated from the light emitting layer from moving to an electron injection layer or an electron injection material, and is also excellent in an ability to form a thin film. Preferably, the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is a value 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 metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanenitrile-based hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinones, polyaniline-based and polythiophene-based conductive polymers, and the like, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. The hole transport material is suitably a material having high hole mobility that can receive holes from the positive electrode or the hole injection layer and transfer the holes to the light emitting layer. Specific examples of the hole transport material include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like, but are not limited thereto.

The hole-regulating layer is a layer that prevents electrons from flowing from the light-emitting layer to the positive electrode, and regulates the performance of the entire device by regulating the flow of holes to the light-emitting layer. The hole-regulating material is preferably a compound of: which has the ability to prevent electrons from flowing from the light-emitting layer to the positive electrode and the ability to regulate the flow of holes to be injected into the light-emitting layer or the light-emitting material. In one exemplary embodiment, as the electron blocking layer, an arylamine-based organic material may be used, but the electron blocking layer is not limited thereto.

The light emitting material is a material that can receive holes and electrons from the hole transport layer and the electron transport layer and combine the holes and the electrons to emit light in the visible light region, and is preferably a material having high quantum efficiency for fluorescence or phosphorescence. In one exemplary embodiment of the present invention, the light emitting layer includes a compound represented by formula 1.

In one exemplary embodiment, the light emitting layer including the compound represented by formula 1 may further include other light emitting materials in the light emitting layer, or the light emitting layer not including the compound represented by formula 1 may include other light emitting materials. Specific examples of other luminescent materials include: 8-hydroxyquinoline aluminum complex (Alq)₃) (ii) a A carbazole-based compound; a di-polystyrene based compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; based on benzeneAzole, benzothiazole-and benzimidazole-based compounds(ii) a Polymers based on poly (p-phenylene vinylene) (PPV); a spiro compound; a polyfluorene; rubrene; and the like, but are not limited thereto.

In one exemplary embodiment, the light emitting layer may include a host material and a dopant material. Examples of the host material include a fused aromatic ring derivative or a heterocyclic ring-containing compound and the like. Specifically, examples of the fused aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but examples thereof are not limited thereto. In one exemplary embodiment, the compound represented by formula 1 may be used as a host material of a light emitting layer.

Examples of the dopant material of the light-emitting layer include aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, and pyrene, anthracene, a derivative having an arylamine group, a derivative having a fused aromatic ring, and the like can be used,Diindenopyrene, and the like. As the styrene amine compound, a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine may be used. Examples of the styrene amine compound include styrene amine, styrene diamine, styrene triamine, styrene tetramine, and the like, but are not limited thereto. As the metal complex, an iridium complex, a platinum complex, and the like can be used, but the metal complex is not limited thereto.

The electron adjusting layer is a layer which blocks the flow of holes from the light emitting layer to the negative electrode, and adjusts the performance of the entire device by adjusting the flow of electrons to the light emitting layer. The electron-regulating material is preferably a compound of: which has the ability to prevent holes from flowing from the light-emitting layer to the negative electrode and the ability to regulate the flow of electrons to be injected into the light-emitting layer or the light-emitting material. As the electron adjusting material, an appropriate material may be used according to the configuration of the organic material layer used in the device. The electron-regulating layer is located between the light-emitting layer and the negative electrode, and is preferably disposed in direct contact with the light-emitting layer.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer. The electron transport material is suitably a material having high electron mobility that can skillfully receive electrons injected from the negative electrode and transfer the electrons to the light emitting layer. Examples of the electron transport material include: al complexes of 8-hydroxyquinoline; comprising Alq₃The complex of (1); an organic radical compound; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired negative electrode material as used according to the related art. In one exemplary embodiment, as the negative electrode material, a material having a low work function may be used; and an aluminum or silver layer. Examples of the material having a low work function include cesium, barium, calcium, ytterbium, samarium, and the like, and after a layer is formed by using the material, an aluminum layer or a silver layer may be formed on the layer.

The electron injection layer is a layer that injects electrons received from the electrode into the light emitting layer. As the electron injecting material, a compound of: it has an ability to transport electrons, an effect of injecting electrons from a negative electrode, and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated from the light emitting layer from moving to a hole injection layer, and is also excellent in an ability to form a thin film. Specific examples thereof include fluorenones, anthraquinone dimethanes, diphenoquinones, thiopyran dioxides, and the like,Azole,Oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

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

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

EMBODIMENTS FOR CARRYING OUT THE INVENTION

Hereinafter, the present specification will be described in detail with reference to examples for specifically describing the present specification. However, the embodiments according to the present specification may be modified in various forms, and it should not be understood that the scope of the present application is limited to the embodiments described in detail below. The embodiments of the present application are provided to more fully explain the present specification to those of ordinary skill in the art.

< preparation example >

The compound represented by formula 1 may be formed by introducing various types of substituents substituted with deuterium as described below. The various compounds in the specific examples were synthesized by the following preparation methods.

Preparation examples 1 to 1: synthesis of Compound 1

10g (60.9mmol) of 2, 5-difluoroterephthalonitrile, 122mmol of 9H-carbazole-1, 2,3,4-d4, 100mL of Dimethylformamide (DMF) and 244mmol of potassium carbonate were mixed, and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 1(25.6g) (yield 90%).

MS[M+H]+＝467

Preparation examples 1 to 2: synthesis of Compound 2

12.2g (60.9mmol) of 2,3,5, 6-tetrafluoroterephthalonitrile, 243.6mmol of 9H-carbazole-1, 2,3,4-d4, 120mL of DMF and 487mmol of potassium carbonate were mixed, and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 2(39.7g) (yield 81%).

MS[M+H]+＝805

Preparation examples 1 to 3: synthesis of Compound 3

12.2g (60.9mmol) of 2,4,5, 6-tetrafluoroisophthalonitrile, 243.6mmol of 9H-carbazole-4-d, 120mL of DMF and 487mmol of potassium carbonate were mixed, and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 3(40.1g) (yield 83%).

MS[M+H]+＝793

Preparation examples 1 to 4: synthesis of Compound 4

11.1g (60.9mmol) of 2,4, 6-trifluoroisophthalonitrile, 182.7mmol of 9H-carbazole-1-d, 110mL of DMF and 365.4mmol of potassium carbonate were mixed, and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 4(30.5g) (yield 80%).

MS[M+H]+＝627

Preparation examples 1 to 5: synthesis of Compound 5

12.2g (60.9mmol) of 2,4,5, 6-tetrafluoroisophthalonitrile, 243.6mmol of 9H-carbazole-2, 4,5,7-d4, 120mL of DMF and 487mmol of potassium carbonate were mixed, and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 5(37.8g) (yield 77%).

MS[M+H]+＝807

Preparation examples 1 to 6: synthesis of Compound 6

10g (60.9mmol) of 3, 6-difluorophthalonitrile, 121.8mmol of 3- (phenyl-d 5) -9H-carbazole, 100mL of DMF and 243.6mmol of potassium carbonate were mixed and the mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 6(31.7g) (yield 84%).

MS[M+H]+＝621

Preparation examples 1 to 7: synthesis of Compound 7

22.6g (60.9mmol) of 5- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -2, 4-difluorobenzonitrile, 121.8mmol of 9H-carbazole-2, 4,5,7-d4, 200mL of DMF and 243.6mmol of potassium carbonate are mixed, and the resulting mixture is heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 7(33.2g) (yield 81%).

MS[M+H]+＝673

Preparation examples 1 to 8: synthesis of Compound 8

22.1g (60.9mmol)2, 4-diphenyl-6- (3,4, 5-trifluorophenyl) -1,3, 5-triazine, 182.7mmol 3, 6-bis (methyl-d 3) -9H-carbazole, 220mL DMF and 365.4mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 8(44.1g) (yield 83%).

MS[M+H]+＝873

Preparation examples 1 to 9: synthesis of Compound 9

14.7g (60.9mmol)2, 6-difluoro-4-phenylpyridine-3, 5-dicarbonitrile, 121.8mmol3- (methyl-d 3) -9H-carbazole, 150mL DMF and 243.6mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 9(25.3g) (yield 73%).

MS[M+H]+＝570

Preparation examples 1 to 10: synthesis of Compound 10

21.5g (60.9mmol)3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -4-fluorobenzonitrile, 60.9mmol 2- (phenyl-d 5) -9H-carbazole, 220mL DMF and 121.8mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 10(25.1g) (yield 71%).

MS[M+H]+＝581

Preparation examples 1 to 11: synthesis of Compound 11

27.9g (60.9mmol)5- (4- (dibenzo [ b, d ] thiophen-2-yl) -6-phenyl-1, 3, 5-triazin-2-yl) -2-fluorobenzonitrile, 60.9mmol 5- (phenyl-d 5) -5, 12-indolino [3,2-a ] carbazole, 280mL DMF and 121.8mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 11(38.3g) (yield 81%).

MS[M+H]+＝776

Preparation examples 1 to 12: synthesis of Compound 12

44.3g (60.9mmol)3- (4- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -4-fluorophenyl-2, 5,6-d3) -6-phenyl-1, 3, 5-triazin-2-yl) -9-phenyl-9H-carbazole, 60.9mmol 5- (9, 9-dimethyl-9H-fluoren-2-yl) -5, 12-dihydroindolo [3,2-a ] carbazole, 400mL DMF and 121.8mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 12(49.2g) (yield 70%).

MS[M+H]+＝1155

Preparation examples 1 to 13: synthesis of Compound 13

31.7g (60.9mmol) 4-fluoro-3- (4-phenyl-6- (9-phenyl-9H-carbazol-3-yl) -1,3, 5-triazin-2-yl) benzonitrile-2, 5,6-d3, 60.9mmol 5-phenyl-5, 12-dihydroindolo [3,2-a ] carbazole, 300mL DMF and 121.8mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 13(34.5g) (yield 68%).

MS[M+H]+＝833

Preparation examples 1 to 14: synthesis of Compound 14

40.7g (60.9mmol)2- (dibenzo [ b, d ] thiophen-2-yl) -4- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -4-fluorophenyl-2, 5,6-d3) -6-phenyl-1, 3, 5-triazine, 60.9mmol 5- (dibenzo [ b, d ] furan-2-yl) -5, 12-dihydroindolo [3,2-a ] carbazole, 350mL DMF and 121.8mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 14(46.9g) (yield 72%).

MS[M+H]+＝1070

Preparation examples 1 to 15: synthesis of Compound 15

22.1g (60.9mmol) of 5- (4, 6-bis (phenyl-d 5) -1,3, 5-triazin-2-yl) -2-fluorobenzonitrile, 60.9mmol of 5-phenyl-5, 12-indolino [3,2-a ] carbazole, 220mL of DMF and 121.8mmol of potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 15(35.7g) (yield 87%).

MS[M+H]+＝675

Preparation examples 1 to 16: synthesis of Compound 16

27.2g (60.9mmol)3- (4- (dibenzo [ b, d ] furan-2-yl) -6- (phenyl-d 5) -1,3, 5-triazin-2-yl) -4-fluorobenzonitrile, 60.9mmol 5-phenyl-5, 12-indolino [3,2-a ] carbazole, 250mL DMF and 121.8mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 16(35.2g) (yield 76%).

MS[M+H]+＝760

Preparation examples 1 to 17: synthesis of Compound 17

20.5g (60.9mmol)2- (4-fluorophenyl) -4, 6-bis (phenyl-d 5) -1,3, 5-triazine, 60.9mmol 9'H-9,3':6', 9' -terparbazole, 200mL DMF and 121.8mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 17(36.2g) (yield 73%).

MS[M+H]+＝815

Preparation examples 1 to 18: synthesis of Compound 18

35.2g (60.9mmol)6,6' - (4-fluoro-1, 3-phenylene) bis (2, 4-bis (phenyl-d 5) -1,3, 5-triazine), 60.9mmol 5- (dibenzo [ b, d ] thiophen-2-yl) -5, 12-dihydroindolo [3,2-a ] carbazole, 300mL DMF and 121.8mmol potassium carbonate were mixed and the resulting mixture was heated to 100 ℃ and stirred for 3 hours. After the reaction, a solid was obtained by filtering the reaction solution cooled to room temperature, and then the solid was recrystallized twice from tetrahydrofuran and ethanol to obtain compound 18(45.5g) (yield 75%).

MS[M+H]+＝997

< comparative example 1-1>

Thinly coated with a thickness ofThe glass substrate of Indium Tin Oxide (ITO) of (1) was put in distilled water in which a detergent was dissolved, and ultrasonic washing was performed. In this case, a product manufactured by Fischer co. was used as a cleaning agent, and distilled water filtered twice using a filter manufactured by Millipore co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeatedly performed twice for 10 minutes by using distilled water. After the completion of the washing with distilled water, the substrate was ultrasonically washed with isopropyl alcohol, acetone and methanol solvents, dried, and then transferred to a plasma cleaner. Further, the substrate was cleaned for 5 minutes by using oxygen plasma and then conveyed to a vacuum deposition machine. By vacuum deposition at 5.0X 10^-4Each thin film was stacked on the thus prepared ITO transparent electrode under a vacuum degree of Pa. First, hexaazatriphenylene-hexacarbonitrile (HAT-CN) is thermally vacuum deposited on ITO to haveThereby forming a hole injection layer.

Vacuum depositing the following compound NPB on the hole injection layer to form a hole transport layer

The following compound EB1 was vacuum deposited on the hole transport layer to haveTo form an electron blocking layer

Subsequently, the following m-CBP and 4CzIPN were vacuum-deposited on the electron blocking layer at a weight ratio of 70:30 to haveThereby forming a light emitting layer.

The following compound HB1 was vacuum-deposited on the light-emitting layer to haveThereby forming a hole blocking layer.

The following compound ET1 and compound lithium quinoline (LiQ) were vacuum deposited on the hole blocking layer at a weight ratio of 1:1 to form a thickness ofElectron injection and transport layers. Sequentially depositing lithium fluoride (LiF) and aluminum on the electron injecting and transporting layer to a thickness ofAndthereby forming a negative electrode.

In the preceding step, the deposition rate of the organic material is maintained atToThe deposition rates of lithium fluoride and aluminum of the negative electrode are respectively maintained atAndduring depositionThe degree of hollowness is kept at 2 x 10^-7Hold in the palm to 5 x 10^-6And supporting to thereby manufacture an organic light emitting device.

< Experimental examples 1-1 to 1-18>

An organic light-emitting device was fabricated in the same manner as in comparative example 1-1, except that the compound of table 1 below was used instead of the compound 4CzIPN in comparative example 1-1.

< comparative examples 1-2 to 1-7>

An organic light-emitting device was fabricated in the same manner as in comparative example 1-1, except that the following compounds T1 to T6 were used in place of the compound 4CzIPN in comparative example 1-1.

For each of the organic light emitting devices of Experimental examples 1-1 to 1-18 and comparative examples 1-1 to 1-7, at 10mA/cm²The drive voltage (V) and the current efficiency (cd/A) were measured at a current density of 3000cd/m²Measured at a luminance of 3000cd/m, and measured at a CIE color coordinate of²The time taken for the lower brightness to decrease to 95% (T95), the results of which are shown in table 1 below.

[ Table 1]

As shown in table 1, the devices of experimental examples 1-1 to 1-18 in which the compound of formula 1 was used had lower voltage and more improved efficiency than the device of comparative example 1-1 in which the material of compound 4CzIPN was used. Further, it can be seen that the characteristics of the devices in which the compound of formula 1 was used were improved in all of voltage, efficiency and color purity, as compared with the devices of comparative examples 1-2 to 1-7.

Therefore, it can be confirmed that the compound according to the present invention is excellent in light emitting ability and has high color purity, and thus can be applied to a delayed fluorescence organic light emitting device.

< comparative example 2-1>

Thinly coated with a thickness ofThe glass substrate of Indium Tin Oxide (ITO) of (1) was put in distilled water in which a detergent was dissolved, and ultrasonic washing was performed. In this case, a product manufactured by Fischer co. was used as a cleaning agent, and distilled water filtered twice using a filter manufactured by Millipore co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeatedly performed twice for 10 minutes by using distilled water. After the completion of the washing with distilled water, the substrate was ultrasonically washed with isopropyl alcohol, acetone and methanol solvents, dried, and then transferred to a plasma cleaner. Further, the substrate was cleaned for 5 minutes by using oxygen plasma and then conveyed to a vacuum deposition machine. By vacuum deposition at 5.0X 10^-4Each thin film was stacked on the thus prepared ITO transparent electrode under a vacuum degree of Pa. First, hexaazatriphenylene-hexacarbonitrile (HAT-CN) is thermally vacuum deposited on ITO to haveThereby forming a hole injection layer.

Vacuum depositing the following compound NPB on the hole injection layer to form a hole transport layer

The following compound EB1 was vacuum deposited on the hole transport layer to haveTo form an electron blocking layer

Subsequently, the following compounds m-CBP, 4CzIPN and GD1 were vacuum deposited on the electron blocking layer at a weight ratio of 68:30:2 to haveThereby forming a light emitting layer.

The following compound HB1 was vacuum-deposited on the light-emitting layer to haveThereby forming a hole blocking layer.

The following compound ET1 and compound lithium quinoline (LiQ) were vacuum deposited on the hole blocking layer at a weight ratio of 1:1 to form a thickness ofElectron injection and transport layers. Sequentially depositing lithium fluoride (LiF) and aluminum on the electron injecting and transporting layer to a thickness ofAndthereby forming a negative electrode.

In the preceding step, the deposition rate of the organic material is maintained atToThe deposition rates of lithium fluoride and aluminum of the negative electrode are respectively maintained atAndthe degree of vacuum during deposition was maintained at 2X 10^-7Hold in the palm to 5 x 10^-6And supporting to thereby manufacture an organic light emitting device.

< Experimental examples 2-1 to 2-18>

An organic light emitting device was fabricated in the same manner as in comparative example 2-1, except that the compound in table 2 below was used instead of the compound 4CzIPN in comparative example 2-1.

< comparative examples 2-2 to 2-7>

An organic light emitting device was fabricated in the same manner as in comparative example 2-1, except that the compound in table 2 below was used instead of the compound 4CzIPN in comparative example 2-1.

For each of the organic light emitting devices of Experimental examples 2-1 to 2-18 and comparative examples 2-1 to 2-7, at 10mA/cm²The drive voltage (V) and the current efficiency (cd/A) were measured at a current density of (1), and was set at 3000cd/m²Measured for CIE color coordinates at brightness, the results of which are shown in table 2 below.

[ Table 2]

As shown in table 2, the devices of experimental examples 2-1 to 2-18 in which the compound of formula 1 was used had lower voltage and more improved efficiency than the device of comparative example 2-1 in which the material of compound 4CzIPN was used. Further, it can be seen that the characteristics of the devices in which the compound of formula 1 was used were improved in both voltage and efficiency, as compared with the devices of comparative examples 2-1 to 2-7.

Therefore, it can be confirmed that the compound according to the present invention is excellent in light-emitting ability, emission wavelength can be adjusted, and thus an organic light-emitting device having high color purity can be realized.