KR102454041B1 - Delayed Fluorescence compound, and Organic light emitting diode device and Display device using the same - Google Patents

Abstract

The present invention provides an electron donor moiety selected from carbazole, phenylcarbazole, acridine or phenylacridine on the benzene ring of the benzo[4,5]thieno[2,3-b]quinoxaline electron acceptor moiety. Provided is a delayed fluorescence compound having a molecular formula of a structure to which T is bound.

Description

Delayed fluorescence compound, organic light emitting diode device and display device including the same

The present invention relates to a light emitting material. More specifically, it relates to a delayed fluorescent compound having improved luminous efficiency by intramolecular charge transfer, an organic light emitting diode device including the same, and a display device.

Recently, as display devices have become larger, the demand for flat display devices that occupy less space is increasing. As one of these flat display devices, the technology of an organic light emitting diode (OLED), also called an organic light emitting diode (OLED), is rapidly increasing. is developing into

The organic light emitting diode device emits light when electrons and holes are injected from the cathode and anode into the light emitting material layer formed between the electron injection electrode (cathode) and the hole injection electrode (anode), the electrons and holes are paired and then disappear. . The device can be formed on a flexible transparent substrate such as plastic, and it can be driven at a low voltage (10V or less), and has the advantage of relatively low power consumption and excellent color.

The organic light emitting diode device includes a first electrode formed on a substrate and serving as an anode, a second electrode spaced apart from and facing the first electrode, and an organic light emitting layer positioned between the first electrode and the second electrode.

In order to improve luminous efficiency, the organic light emitting layer is a hole injection layer (HIL), a hole transport layer (HTL), a light emitting material layer (EML) sequentially stacked on the first electrode. , an electron transporting layer (ETL), and an electron injection layer (EIL).

Holes from the first electrode as the anode move to the light emitting material layer through the hole injection layer and the hole transport layer, and electrons from the second electrode as the cathode move to the light emitting material layer through the electron injection layer and the electron transport layer.

The holes and electrons moved to the light emitting material layer combine to form excitons, and are excited to an unstable energy state and then return to a stable energy state to emit light.

The external quantum efficiency (η _ext ) of the light emitting material used in the light emitting material layer can be obtained by the following equation.

η _ext = η _int ×г × Φ × η _{out - coupling}

(here, η _int : internal quantum efficiency, г: charge balance factor, Φ: radiative quantum efficiency, η _{out - coupling} : out coupling efficiency)

Charge balance factor (г) means the balance between holes and electrons forming excitons, and generally has a value of '1' assuming 100% 1:1 matching. Radiative quantum efficiency (Φ) is a value related to the luminous efficiency of the actual luminescent material, and in the host-dopant system, it depends on the fluorescence quantum efficiency of the dopant.

The internal quantum efficiency (η _int ) is the rate at which generated excitons are converted into the form of light, and in the case of a fluorescent material, it has a limiting value of up to 0.25. When holes and electrons combine to form excitons, singlet excitons and triplet excitons are generated in a ratio of 1:3 depending on the spin arrangement. However, in a fluorescent material, only singlet excitons participate in light emission and the remaining 75% of triplet excitons do not participate in light emission.

Out coupling efficiency (η _{out - coupling} ) is the ratio of the emitted light to the outside. In general, when an isotropic type molecule is thermally deposited to form a thin film, individual light emitting molecules do not have a certain direction and exist in a disordered state. It is generally assumed that the out-coupling efficiency in this random orientation state is 0.2.

Accordingly, the maximum luminous efficiency of the organic light emitting diode device using the fluorescent material is about 5% or less.

In order to overcome the low efficiency problem of fluorescent materials, a phosphor having a light emitting mechanism that converts both singlet excitons and triplet excitons into light has been developed.

In the case of red and green, phosphorescent materials having high luminous efficiency have been developed, but in the case of blue, phosphorescent materials satisfying the required luminous efficiency and reliability have not been developed.

Therefore, in a fluorescent material satisfying reliability, there is a need to develop a material capable of increasing luminous efficiency by increasing quantum efficiency.

The present invention aims to solve the problem of low quantum efficiency of fluorescent materials.

In order to solve the above problems, the present invention provides a delay having a molecular formula of a structure in which an electron donor moiety is bonded to the benzene ring of a benzo [4,5] thieno [2,3-b] quinoxaline electron acceptor moiety. Fluorescent compounds are provided.

The electron donor moiety may be selected from carbazole, phenylcarbazole, acridine or phenylacridine.

That is, the delayed fluorescent compound of the present invention is represented by the following formula, m and n are integers from 0 to 2, m or n is 0, and D1 and D2 are each of carbazole, phenylcarbazole, acridine or phenyla. may be selected from credin.

In addition, the present invention provides an organic light emitting diode device and a display device in which the organic light emitting layer includes the above-described delayed fluorescent compound.

The delayed fluorescence compound of the present invention has a structure in which a benzo[4,5]thieno[2,3-b]quinoxaline electron acceptor moiety and an electron donor moiety are combined, and a molecule The movement of electric charge occurs easily and the luminous efficiency is improved. Therefore, in the delayed fluorescent compound of the present invention, since the exciton in the triplet state is used for light emission, the luminous efficiency of the delayed fluorescent compound is improved.

In particular, benzo [4,5] thieno [2,3-B] quinoxaline with strong electron accepting properties is used as an electron acceptor moiety, and an electron acceptor moiety and an electron donor moiety are included in the molecule, so that the triplet The utilization efficiency of state excitons is increased.

In addition, since carbazole or acridine is used as an electron donor moiety to form a large dihedral angle with benzo[4,5]thieno[2,3-B]quinoxaline, red shift of light emitted from the light emitting layer (red shift) problem can be minimized.

In addition, the electron donor moiety and the electron acceptor moiety are combined in the molecule and the overlap of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) is reduced. Since a field activated delayed fluorescence complex is formed, the luminous efficiency of the delayed fluorescence compound is further improved.

Accordingly, the organic light emitting diode device and the display device including the delayed fluorescent compound of the present invention can improve luminous efficiency and realize high-quality images.

1 is a view for explaining a light emission mechanism of a delayed fluorescent compound according to an embodiment of the present invention.
2a and 2b are each a view showing the HOMO and LUMO distribution of Compound 1 according to the present invention.
3a and 3b are each a view showing the HOMO and LUMO distribution of Compound 2 according to the present invention.
4A and 4B are diagrams showing the HOMO and LUMO distributions of Compound 3 according to the present invention.
5a and 5b are each a view showing the HOMO and LUMO distribution of Compound 4 according to the present invention.
6A and 6B are views showing the HOMO and LUMO distributions of Compound 5 according to the present invention.
7a and 7b are each showing the HOMO and LUMO distribution of Compound 6 according to the present invention.
8A and 8B are diagrams showing the HOMO and LUMO distributions of Compound 7 according to the present invention.
9A and 9B are diagrams showing the HOMO and LUMO distributions of Compound 8 according to the present invention.
10A and 10B are diagrams showing the HOMO and LUMO distributions of Compound 9 according to the present invention.
11A and 11B are diagrams showing the HOMO and LUMO distributions of Compound 10 according to the present invention.
12A and 12B are diagrams showing the HOMO and LUMO distributions of Comparative Compound 1, respectively.
13A and 13B are diagrams showing the HOMO and LUMO distributions of Comparative Compound 2, respectively.
14A and 14B are diagrams showing HOMO and LUMO distributions of Comparative Compound 3, respectively.
15A and 15B are diagrams showing the HOMO and LUMO distributions of Comparative Compound 4, respectively.
16A and 16B are diagrams showing HOMO and LUMO distributions of Comparative Compound 4, respectively.
17A and 17B are diagrams showing HOMO and LUMO distributions of Comparative Compound 4, respectively.
18A to 18C are graphs showing delayed fluorescence characteristics of delayed fluorescent compounds according to an embodiment of the present invention.
19 is a schematic cross-sectional view of an organic light emitting diode device according to an embodiment of the present invention.

The present invention provides an electron donor moiety selected from carbazole, phenylcarbazole, acridine or phenylacridine on the benzene ring of the benzo[4,5]thieno[2,3-b]quinoxaline electron acceptor moiety. Provided is a delayed fluorescence compound having a molecular formula of a structure to which T is bound.

In another aspect, the present invention is represented by the following formula (1), each of D1 and D2 is selected from the following formula (2), m and n are integers from 0 to 2, one of m or n is 0, R1, R2 Each independently provides a delayed fluorescence compound selected from C1-C10 alkyl.

[Formula 1]

[Formula 2]

The delayed fluorescence compound of the present invention may be any one of the following compounds.

In the delayed fluorescent compound of the present invention, the difference between the singlet energy and the triplet energy of the delayed fluorescent compound may be 0.3 eV or less.

In another aspect, the present invention includes a first electrode, a second electrode facing the first electrode, and an organic light emitting layer positioned between the first and second electrodes, wherein the organic light emitting layer comprises: ,5] a molecular formula of a structure in which an electron donor moiety selected from carbazole, phenylcarbazole, acridine or phenylacridine is bonded to the benzene ring of the thieno[2,3-b]quinoxaline electron acceptor moiety It provides an organic light emitting diode device comprising a delayed fluorescent compound having a.

In another aspect, the present invention includes a first electrode, a second electrode facing the first electrode, and an organic light emitting layer positioned between the first and second electrodes, wherein the organic light emitting layer includes the following Chemical Formula 1 D1, D2 each is selected from the following formula (2), m and n are an integer of 0 to 2, any one of m or n is 0, R1, R2 each is independently C1 ~ C10 in alkyl An organic light emitting diode device comprising a selected delayed fluorescence compound is provided.

[Formula 1]

[Formula 2]

In the organic light emitting diode device of the present invention, the delayed fluorescent compound may be any one of the following compounds.

In the organic light emitting diode device of the present invention, the difference between the singlet energy and the triplet energy of the delayed fluorescent compound may be 0.3 eV or less.

In the organic light emitting diode device of the present invention, the delayed fluorescent compound is used as a dopant, and the organic light emitting layer may further include a host.

In the organic light emitting diode device of the present invention, the difference between the highest occupied molecular orbital level of the host (HOMO _Host ) and the highest occupied molecular orbital level of the dopant (HOMO _Dopant ) (|HOMO _Host -HOMO _Dopant |) or the host The difference between the lowest unoccupied molecular orbital level (LUMO _Host ) and the lowest unoccupied molecular orbital level (LUMO _Dopant ) of the dopant (|LUMO _Host -LUMO _Dopant |) may be 0.5 eV or less.

In the organic light emitting diode device of the present invention, the delayed fluorescent compound is used as a host, and the organic light emitting layer may further include a dopant.

In the organic light emitting diode device of the present invention, the delayed fluorescent compound is used as a first dopant, and the organic light emitting layer further includes a host and a second dopant, and the first triplet energy of the first dopant is the first triplet energy of the host. It may be less than the second triplet energy and greater than the third triplet energy of the second dopant.

In another aspect, the present invention includes a substrate, the above-described organic light emitting diode device positioned on the substrate, an encapsulation film covering the organic light emitting diode device, and a cover window on the encapsulation film A display device is provided.

Hereinafter, a structure of a delayed fluorescent compound according to an embodiment of the present invention, a synthesis example thereof, and an organic light emitting diode device using the same will be described.

Delayed fluorescence compound according to an embodiment of the present invention, benzo [4,5] thieno [2,3-b] quinoxaline (benzo [4,5] thieno [2,3-b] quinoxaline) electron acceptor (electron) It has a molecular formula of a structure in which an acceptor) moiety and an electron donor moiety are bonded, and is represented by Formula 1 below.

[Formula 1]

That is, it has a structure in which electron donor moieties D1 and D2 are bonded to the benzene ring of benzo[4,5]thieno[2,3-b]quinoxaline.

In this case, m and n are integers from 0 to 2, and either m or n is 0. That is, the structure in which the electron donor moiety D1 is bonded to the 2nd and 3rd positions of the benzene ring of the quinoxaline moiety of benzo[4,5]thieno[2,3-b]quinoxaline as shown in Formula 2-1 below. or have a structure in which the electron donor moiety D1 is bonded to the benzene ring 2 position of the quinoxaline moiety of benzo[4,5]thieno[2,3-b]quinoxaline as shown in Formula 2-2 below can In addition, the electron donor moiety D2 is located at the 2nd and 3rd positions of the benzene ring of the benzothiophene moiety of benzo[4,5]thieno[2,3-b]quinoxaline as shown in Formula 2-3 below. has a bonded structure, or an electron donor moiety D2 at the 2nd position of the benzene ring of the benzothiophene moiety of benzo[4,5]thieno[2,3-b]quinoxaline as shown in Formula 2-4 below It may have a combined structure.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formula 1, each of the electron donor moieties D1 and D2 is selected from carbazole, phenylcarbazole, acridine, or phenylacridine. For example, each of the electron donor moieties D1 and D2 may be selected from the materials represented by Formula 3 below.

[Formula 3]

In Formula 3, each of R1 and R2 may independently be a C1-C10 alkyl.

Such delayed fluorescence compound has a structure in which a benzo[4,5]thieno[2,3-b]quinoxaline electron acceptor moiety and an electron donor moiety are combined, and the charge transfer occurs easily in the molecule and emits light. Efficiency is improved.

That is, the delayed fluorescent compound of the present invention includes both an electron donor moiety and an electron acceptor moiety, so that charge transfer occurs easily in a molecule and luminous efficiency is improved. In addition, since the exciton in the triplet state is used for light emission, the luminous efficiency of the delayed fluorescent compound is improved.

In particular, benzo [4,5] thieno [2,3-B] quinoxaline with strong electron accepting properties is used as an electron acceptor moiety, and an electron acceptor moiety and an electron donor moiety are included in the molecule, so that the triplet The utilization efficiency of state excitons is increased. In addition, since carbazole or acridine is used as an electron donor moiety to form a large dihedral angle with benzo[4,5]thieno[2,3-B]quinoxaline, red shift of light emitted from the light emitting layer (red shift) problem can be minimized.

In addition, the electron donor moiety and the electron acceptor moiety are combined in the molecule and the overlap of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) is reduced. Since the field activation complex is formed, the luminous efficiency of the delayed fluorescent compound is further improved.

Referring to FIG. 1, which is a diagram for explaining the light emission mechanism of the delayed fluorescent compound according to an embodiment of the present invention, in the delayed fluorescent compound of the present invention, both singlet excitons and triplet excitons participate in light emission to improve quantum efficiency. do.

That is, in the delayed fluorescent compound of the present invention, triplet excitons are activated by an electric field, triplet excitons and singlet excitons move to an intermediate state (I ₁ ), and the ground state (S _{0 )} ) and emits light. In other words, a transition occurs from the singlet state (S ₁ ) and the triplet state (T ₁ ) to the intermediate state (I ₁ ) (S ₁ -> I ₁ <-T ₁ ), both singlet and triplet excitons. By participating in light emission, the light emission efficiency is improved. This is referred to as a FADF (filed activated delayed fluorescence) compound.

In conventional fluorescent materials, interconversion between singlet and triplet states is impossible because HOMO and LUMO are spread throughout the molecule. (selection rule)

However, in the FADF compound as in the present invention, since the intramolecular HOMO and LUMO overlap is small, the interaction between HOMO and LUMO is small. Accordingly, the change in the spin state of an electron does not affect other electrons, and a new charge transfer band that does not follow the selection rule is formed.

In addition, since the electron acceptor moiety and the electron donor moiety are spaced apart from each other in the molecule, an intramolecular dipole moment exists in a polarized form. In a state where the dipole moment is polarized, the interaction between the HOMO and the LUMO becomes small and the selection rule may not be followed. Therefore, in the FADF compound, the transition from the triplet state (T ₁ ) and the singlet state (S ₁ ) to the intermediate state (I ₁ ) is possible, and the triplet exciton participates in light emission.

When the organic light emitting diode device is driven, 25% of singlet state (S ₁ ) excitons and 75% of triplet state (T ₁ ) excitons cause a transition to the intermediate state (I ₁ ) and the ground state (S) by an electric field. The internal quantum efficiency becomes 100% theoretically because luminescence occurs as it drops to ₀ ).

For example, the delayed fluorescence compound of Formula 1 may be any one of the compounds of Formula 4 below.

[Formula 4]

The delayed fluorescence compound of the present invention contains benzo [4,5] thieno [2,3-b] quinoxaline as an electron accepting moiety, and includes carbazole, phenylcarbazole, acridine ( acridine) or phenylacridine (phenylacridine), since the electron donor moiety is included, the luminous efficiency of the triplet state exciton is increased and the color is improved.

2a to 17b are diagrams showing the HOMO and LUMO distributions of compounds 1 to 16 of Formula 4, and the HOMO, LUMO, and bandgap energies of these compounds are described in Table 1.

As shown in FIGS. 2A to 17B and Table 1, in the delayed fluorescent compound of the present invention, HOMO and LUMO separation occurs well and has an energy bandgap of 3.5 eV or more. Accordingly, the triplet state exciton becomes a FADF compound that participates in light emission and emits deep blue light.

Hereinafter, a synthesis example of a delayed fluorescent compound according to an embodiment of the present invention will be described.

-Synthesis example-

1. Synthesis of compound 1

(1) Synthesis of compound C

[Scheme 1-1]

Under a nitrogen environment (N2 purging), compound A was dissolved in diethyl ether, and 1.2 equivalents of compound B (dissolved in MC) was slowly dropped at 0°C. After stirring at room temperature for 3 hours, 3 equivalents of alumimium chloride was slowly dropped at 0°C. After stirring for 12 hours, HCl 1M solution was slowly added to terminate the reaction and extraction was performed. Compound C in a white solid state was obtained through a short-column using hexane.

(2) Synthesis of compound E

[Scheme 1-2]

Under a nitrogen environment (N2 purging), compound C and 1.5 equivalents of compound D were added to acetic acid and stirred at 90°C. After 16 hours, water was added to terminate the reaction and extraction was performed. By precipitation using MC and hexane, compound E in a white solid state was obtained.

(3) Synthesis of compound 1

[Scheme 1-3]

Under a nitrogen environment (N2 purging), Compound E, 1.2 equivalents of Compound F, 1.0 equivalent of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane and stirred in an oil bath at 90°C. After 14 hours, water was added to the reaction mixture, followed by extraction. Compound 1 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (9:1).

2. Synthesis of compound 2

(1) Synthesis of compound H

[Scheme 2-1]

Under a nitrogen environment (N2 purging), compound C and 1.5 equivalents of compound G were added to acetic acid and stirred at 90°C. After 16 hours, water was added to terminate the reaction and extraction was performed. By precipitation using MC and hexane, compound H in a white solid state was obtained.

(2) Synthesis of compound 2

[Scheme 2-2]

Under nitrogen environment (N2 purging), Compound H, 2.3 equivalents of Compound F, 1.0 equivalent of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane and stirred in an oil bath at 90°C. After 18 hours, water was added to the reaction mixture and extracted. Compound 2 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (3:1).

3. Synthesis of compound 3

[Scheme 3]

Under a nitrogen environment (N2 purging), Compound E, 1.3 equivalents of Compound I, 0.05 equivalents of Pd(0), and 4.0 equivalents of potassium carbonate were added to toluene and stirred in an oil bath at 80°C. After 12 hours, water was added to the reaction mixture and extracted. Compound 3 as a white solid was obtained through a column using an electric field solvent of Hexane:MC (4:1).

4. Synthesis of compound 4

[Scheme 4]

Under a nitrogen environment (N2 purging), compound h, 2.3 equivalents of compound I, 0.05 equivalents of Pd(0), and 4.0 equivalents of potassium carbonate were added to toluene and stirred in an oil bath at 80°C. After 16 hours, water was added to the reaction mixture, followed by extraction. Compound 4 in a white solid state was obtained through a column using an electric field solvent of Hexane:EA (4:1).

5. Synthesis of compound 5

(1) Synthesis of compound K

[Scheme 5-1]

Under a nitrogen environment (N2 purging), compound J was dissolved in diethyl ether, and 1.2 equivalents of compound B (dissolved in MC) was slowly dropped at 0°C. After stirring at room temperature for 3 hours, 3 equivalents of alumimium chloride was slowly dropped at 0°C. After stirring for 12 hours, HCl 1M solution was slowly added to terminate the reaction and extraction was performed. Compound K in a white solid state was obtained through a short-column using hexane.

(2) Synthesis of compound M

[Scheme 5-2]

Under a nitrogen environment (N2 purging), compound K and 1.5 equivalents of compound L were added to acetic acid and stirred at 90°C. After 16 hours, water was added to terminate the reaction and extraction was performed. By precipitation using MC and hexane, compound M in a white solid state was obtained.

(3) Synthesis of compound 5

[Scheme 5-3]

Under a nitrogen environment (N2 purging), compound M, 1.2 equivalents of compound F, 1.0 equivalents of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane and stirred in an oil bath at 90°C. After 12 hours, water was added to the reaction mixture and extracted. Compound 5 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (5:1).

6. Synthesis of compound 6

(1) Synthesis of compound O

[Scheme 6-1]

Under a nitrogen environment (N2 purging), compound N was dissolved in diethyl ether, and 1.2 equivalents of compound B (dissolved in MC) was slowly dropped at 0°C. After stirring at room temperature for 3 hours, 3 equivalents of alumimium chloride was slowly dropped at 0°C. After stirring for 12 hours, HCl 1M solution was slowly added to terminate the reaction and extraction was performed. Compound O in a white solid state was obtained through a short-column using hexane.

(2) Synthesis of compound P

[Scheme 6-2]

Under a nitrogen environment (N2 purging), compound O and 1.5 equivalents of compound L were added to acetic acid and stirred at 90°C. After 16 hours, water was added to terminate the reaction and extraction was performed. By precipitation using MC and hexane, compound P in a white solid state was obtained.

(3) Synthesis of compound 6

[Scheme 6-3]

Under nitrogen environment (N2 purging), compound P, 2.3 equivalents of compound F, 1.0 equivalents of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane and stirred in an oil bath at 90°C. After 18 hours, water was added to the reaction mixture and extracted. Compound 6 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (3:2).

7. Synthesis of compound 7

[Scheme 7]

Under a nitrogen environment (N2 purging), compound M, 1.3 equivalents of compound I, 0.05 equivalents of Pd(0), and 4.0 equivalents of potassium carbonate were added to toluene and stirred in an oil bath at 80°C. After 13 hours, water was added to the reaction mixture, followed by extraction. Compound 7 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (4:1).

8. Synthesis of compound 8

[Scheme 8]

Under a nitrogen environment (N2 purging), compound P, 2.3 equivalents of compound I, 0.05 equivalents of Pd(0), and 4.0 equivalents of potassium carbonate were added to toluene and stirred in an oil bath at 80°C. After 20 hours, water was added to the reaction mixture, followed by extraction. Compound 8 in a white solid state was obtained through a column using an electric field solvent of Hexane:EA (3:1).

9. Synthesis of compound 9

(1) Synthesis of compound R

[Scheme 9-1]

Compound Q (46.9 mmol) was mixed in a methanol solvent and stirred under a nitrogen atmosphere. After further stirring at 0° C. for 10 minutes, thionyl chloride (21.2 mmol) was slowly added thereto. The mixed solution was stirred at 90° C. for at least 12 hours. After completion of the reaction, the solvent was removed and distilled water and ethyl acetate were added for extraction. Moisture was removed from the extracted organic layer using magnesium sulfate. After removing the remaining solvent, wet purification was performed through column chromatography using hexane and ethyl acetate to obtain a dark yellow liquid compound R.

(2) Synthesis of compound S

[Scheme 9-2]

Compound R (38.1 mmol) was stirred in a tetrahydrofuran solvent in a nitrogen atmosphere, and then methyl magnesium bromide (4.6 equivalents) was slowly added thereto. The reaction was stirred at room temperature for 12 hours or more. After completion of the reaction, distilled water was slowly added and extracted using ethyl acetate. Moisture was removed from the organic layer using magnesium sulfate, and the remaining solvent was removed. By wet purification by column chromatography using lexane and ethyl acetate, compound S in a yellow liquid state was obtained.

(3) Synthesis of compound T

[Scheme 9-3]

Compound S (33.1 mmol) was stirred with an excess of phosphoric acid (160 ml) solvent at room temperature. After stirring for at least 16 hours, 200-250 ml of distilled water was slowly added. Then, the mixture was stirred for 0.5-1 hour and the precipitated solid was filtered. The filtered solid was extracted using an aqueous sodium hydroxide solution and a dichloromethane solvent, and moisture was removed from the organic layer using magnesium sulfate. The remaining organic solvent was removed to obtain Compound T in a white solid state.

(4) Synthesis of compound 9

[Scheme 9-4]

Under a nitrogen environment (N2 purging), compound E, 1.2 equivalents of compound T, 1.0 equivalents of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane and stirred in an oil bath at 90°C. After 16 hours, water was added to the reaction mixture, followed by extraction. Compound 9 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (3:1).

10. Synthesis of compound 10

[Scheme 10]

Under a nitrogen environment (N2 purging), compound H, 2.2 equivalents of compound T, 1.0 equivalents of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane and stirred in an oil bath at 90°C. After 18 hours, water was added to the reaction mixture and extracted. Compound 10 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (1:1).

11. Synthesis of compound 11

(1) Synthesis of compound V

[Scheme 11-1]

Under a nitrogen environment (N2 purging), compound T, 0.8 equivalents of compound U, 1.0 equivalents of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane and stirred in an oil bath at 90°C. After 11 hours, water was added to the reaction mixture and extracted. Compound V in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (9:1).

(2) Synthesis of compound W

[Scheme 11-2]

Under a nitrogen environment (N2 purging), compound V, 1.5 equivalents of Bu-Li was added to ether and stirred at -78°C. After 4 hours of reaction, 1.2 equivalents of triethyl borate was added and stirred at -78°C for 30 minutes. The dry ice bath was removed to raise the reaction temperature to room temperature. After 14 hours of reaction, 30 ml of HCl (in DI water) was added and the organic solvent was removed. After all organic solvents were removed, the solid precipitated in water was filtered to obtain Compound W in a white solid state.

(3) Synthesis of compound 11

[Scheme 11-3]

Under a nitrogen environment (N2 purging), Compound E, 1.3 equivalents of Compound W, 0.05 equivalents of Pd(0), and 4.0 equivalents of potassium carbonate were added to toluene and stirred in an oil bath at 80°C. After 11 hours, water was added to the reaction mixture and extracted. Compound 11 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (2:1).

12. Synthesis of compound 12

[Scheme 12]

Under a nitrogen environment (N2 purging), Compound H, 2.3 equivalents of Compound W, 0.05 equivalents of Pd(0), and 4.0 equivalents of potassium carbonate were added to toluene and stirred in an oil bath at 80°C. After 16 hours, water was added to the reaction mixture, followed by extraction. Compound 12 in a white solid state was obtained through a column using an electric field solvent of Hexane:EA (3:1).

13. Synthesis of compound 13

[Scheme 13]

Under nitrogen environment (N2 purging), compound M, 1.2 equivalents of compound T, 1.0 equivalents of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane and stirred in an oil bath at 90°C. After 12 hours, water was added to the reaction mixture and extracted. Compound 13 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (4:1).

14. Synthesis of compound 14

[Scheme 14]

Under nitrogen environment (N2 purging), compound P, 2.3 equivalents of compound T, 1.0 equivalents of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane and stirred in an oil bath at 90°C. After 18 hours, water was added to the reaction mixture and extracted. Compound 14 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (1:1).

15. Synthesis of compound 15

[Scheme 15]

Under a nitrogen environment (N2 purging), compound M, 1.3 equivalents of compound W, 0.05 equivalents of Pd(0), and 4.0 equivalents of potassium carbonate were added to toluene and stirred in an oil bath at 80°C. After 13 hours, water was added to the reaction mixture, followed by extraction. Compound 15 in a white solid state was obtained through a column using an electric field solvent of Hexane:MC (3:1).

16. Synthesis of compound 16

[Scheme 16]

Under a nitrogen environment (N2 purging), compound P, 2.3 equivalents of compound W, 0.05 equivalents of Pd(0), and 4.0 equivalents of potassium carbonate were added to toluene and stirred in an oil bath at 80°C. After 20 hours, water was added to the reaction mixture, followed by extraction. Compound 16 in a white solid state was obtained through a column using an electric field solvent of Hexane:EA (3:1).

The mass spectrometry results of compounds 1 to 16 are shown in Table 2.

Using Quantarus tau equipment manufactured by Hamamatsu, the luminescence properties of the following compound (Ref) and the compounds 1 and 5 (Com1, Com5) were measured under O ₂ free conditions, and the measurement results are shown in Table 3 and FIGS. 18a and 18c. described.

[Formula 5]

As shown in Table 3 and Figure 18a, the compound (Ref) of Formula 5 showed delayed fluorescence of several hundred nano-seconds (ns), whereas as shown in Table 3 and Figures 18b and 18c, Compound 1 and compound 5 (Com1, Com5) showed delayed fluorescence of tens of thousands of nano-seconds (ns), respectively.

As described above, the delayed fluorescent compound of the present invention is field activated so that singlet state (S ₁ ) excitons and triplet state (T ₁ ) excitons are transitioned to an intermediate state (I ₁ ), and both of them emit light. participate in

Such an electric field activation complex is a monomolecular compound having an electron donor moiety and an electron acceptor moiety in one molecule at the same time, and the movement of electrons in the molecule occurs easily. In field-activated complexes, electrons are transferred from an electron donor moiety to an electron acceptor moiety under certain conditions, so that separation of charges can occur in a molecule.

The electric field activation complex is formed by the external environment, which can be easily confirmed by comparing the absorption wavelength and the emission wavelength in a solution state using various solvents.

In the above equation, Δν is the stock shift value, and νabs and νfl are the wavenumbers of the maximum absorption wavelength and the maximum emission wavelength, respectively. Also, h is the Plank's constant, c is the velocity of light, a is the onsager cavity radius, and Δμ is the difference between the dipole moment of the excited state and the dipole moment of the ground state (Δμ = μ _e -μ _g ).

Δf is a value indicating the orientational polarizability of the solvent, and is expressed by the dielectric constant (ε) and the refractive index (n) of the solvent as shown in the following equation.

Whether or not the field activation complex is formed can be confirmed by comparing the absorption wavelength and the emission wavelength in a solution state using various solvents. This is because the degree of polarization (dipole moment magnitude) when excitation is determined by the surrounding polarity.

Directional polarization of the mixed solvent, Δf, can be used by calculating the directional polarization values of the pure solvent as a ratio of mole fraction, and the presence or absence of the formation of an electric field activation complex can be determined using the above equation (Lippert-Mataga equation) to determine Δf and Δμ It can be judged by checking whether a linear relationship appears when plotting .

That is, the field-activated complex is stabilized according to the directional polarization degree of the solvent, and the emission wavelength shifts to a longer wavelength according to the stabilization degree. Accordingly, when the field-activated complex is formed, Δf and Δμ form a linear graph, and conversely, when Δf and Δμ form a linear graph, it can be seen that the light-emitting material is a field-activated complex.

In the delayed fluorescent compound of the present invention, 25% of singlet state excitons and 75% of triplet state excitons are intermediate between the singlet state and the triplet state by an external environment, for example, an electromagnetic field generated when an organic light emitting diode device is driven. It is interpreted as causing an intersystem crossing to the state, and the quantum efficiency is improved because light emission occurs as the intermediate state becomes the ground state. That is, in the fluorescent material, not only singlet state excitons but also triplet state excitons participate in light emission, so that luminous efficiency is improved.

Hereinafter, the performance of the organic light emitting diode device using the delayed fluorescent compound of the present invention and the organic light emitting diode device using the comparative compound of Formula 5 will be described in comparison.

device fabrication

After patterning so that the emission area of the ITO substrate was 3 mm X 3 mm in size, it was washed. Next, the substrate was transferred into a vacuum deposition chamber. After making the base pressure to be about 10 ^-6 ~ 10 ^-7 Torr, on the anode, ITO, i) a hole injection layer 40Å (NPB(N,N'-di(naphthalen-1-yl)-N,N'-diphenyl) -benzidine)), ii) hole transport layer 10Å (mCP(N,N'-Dicarbazolyl-3,5-benzene)), iii) light emitting material layer 200Å (host (bis{2-[di(phenyl)phosphino]phenyl} ether oxide/dopant (12%)), iv) electron transport layer 300Å (1,3,5-tri(phenyl-2-benzimidazole)-benzene), v) electron injection layer 10Å (LiF), vi) cathode (Al) were sequentially stacked.

(1) Experimental Example 1 (Ex1)

In the above device, Compound 1 was used as a dopant in the light emitting material layer.

(2) Experimental Example 2 (Ex2)

In the above device, Compound 2 was used as a dopant in the light emitting material layer.

(3) Experimental Example 3 (Ex3)

In the device described above, compound 5 was used as a dopant in the light emitting material layer.

(4) Experimental Example 4 (Ex4)

In the device described above, compound 6 was used as a dopant in the light emitting material layer.

(5) Experimental Example 5 (Ex5)

In the device described above, compound 9 was used as a dopant in the light emitting material layer.

(6) Experimental Example 6 (Ex6)

In the device described above, compound 10 was used as a dopant of the light emitting material layer.

(7) Experimental Example 7 (Ex7)

In the device described above, compound 13 was used as a dopant in the light emitting material layer.

(8) Experimental Example 8 (Ex8)

In the device described above, compound 14 was used as a dopant of the light emitting material layer.

(9) Comparative Example (Ref)

In the above-described device, the compound (Ref) of Formula 5 was used as a dopant of the light emitting material layer.

As shown in Table 4, in the device using the delayed fluorescent compound of the present invention, color (or color purity) and luminous efficiency were improved. That is, even in a compound containing carbazole as an electron donor moiety, its properties vary greatly depending on the electron acceptor moiety, and as in the present invention, benzo [4,5] thieno [2,3- When b] quinoxaline (benzo [4,5] thieno [2,3-b] quinoxaline) is included, the color is improved and, in particular, the luminous efficiency is greatly improved as triplet excitons participate in luminescence.

An example of an organic light emitting diode device including the delayed fluorescent compound is shown in FIG. 19 .

As shown, the organic light emitting diode device includes a light emitting diode E positioned on a substrate (not shown).

The light emitting diode E includes a first electrode 110 serving as an anode, a second electrode 130 serving as a cathode, and an organic light emitting layer 120 formed between the first and second electrodes 110 and 130 . is made of

Meanwhile, although not shown, a display device may be formed by including an encapsulation film including an inorganic layer and an organic layer and covering the light emitting diode E, and a cover window on the encapsulation film. In this case, the substrate and the cover window may have flexible characteristics, thereby forming a flexible display device.

The first electrode 110 is made of a material having a relatively high work function value, for example, indium-tin-oxide (ITO), and the second electrode 130 is made of a material having a relatively low work function value, for example, For example, it is made of aluminum (Al) or an aluminum alloy (AlNd). In addition, the organic light emitting layer 120 is formed of red, green, and blue organic light emitting patterns.

The organic light emitting layer 120 may have a single-layer structure, or in order to improve luminous efficiency, the organic light emitting layer 120 may have a multi-layer structure. For example, sequentially from the first electrode 110 , a hole injection layer (HIL) 121 , a hole transporting layer (HTL) 122 , and an emitting material layer (EML) 123 , an electron transporting layer (ETL) 124 , and an electron injection layer (EIL) 125 .

Here, at least one of the hole injection layer 121, the hole transport layer 122, the light emitting material layer 123, the electron transport layer 124, and the electron injection layer 125 contains the delayed fluorescent compound represented by Formula 1 can be done by

For example, the light emitting material layer 123 may include the delayed fluorescent compound represented by Formula 1 above. The light emitting material layer 123 may include the delayed fluorescent compound of the present invention as a dopant material, and may be doped in an amount of about 1 to 30 wt% with respect to the host, and emit blue light.

The difference between the highest occupied molecular orbital level of the host (HOMO _Host ) and the highest occupied molecular orbital level (HOMO _Dopant ) of the dopant (|HOMO _Host -HOMO _Dopant |) or the lowest unoccupied molecular orbital level of the host (LUMO) _Host ) and the lowest unoccupied molecular orbital level (LUMO _Dopant ) of the dopant (|LUMO _Host -LUMO _Dopant |) is set to be 0.5 eV or less. Accordingly, the efficiency of charge transfer from the host to the dopant is improved.

For example, as a host satisfying such conditions, any one of the following Chemical Formula 6 may be used. (Bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO), 2,8-bis(diphenylphosphoryl)dibenzothiophene (PPT), 2,8-di(9H-carbazol-9-yl)dibenzothiophene (DCzDBT), respectively, m -bis(carbazol-9-yl)biphenyl (m-CBP), Diphenyl-4-triphenylsilylphenyl-phosphine oxide (TPSO1), 9-(9-phenyl-9H-carbazol-6-yl)-9H-carbazole (CCP) )

[Formula 6]

In this case, the triplet energy of the dopant is smaller than the triplet energy of the host, and the difference (ΔE _ST ) between the singlet energy of the dopant and the triplet energy of the dopant is 0.3 eV or less. As ΔE _ST decreases, luminous efficiency increases, and in the delayed fluorescent compound of the present invention, even if the difference (ΔE _ST ) between the singlet energy and the triplet energy of the dopant becomes about 0.3 eV, which is relatively large, the singlet state (S ₁ ) Exciton and triplet state (T ₁ ) An exciton can transition to an intermediate state (I ₁ ). (ΔE _ST ≤0.3)

Meanwhile, the light emitting material layer 123 includes the delayed fluorescent compound of the present invention as a host material, and may include a dopant doped in an amount of about 1 to 30 wt% with respect to the host material, and emits blue light. Since the development of a blue host with excellent properties is not sufficient, the degree of freedom in host selection can be increased by using the delayed fluorescent compound of the present invention as a host material.

In this case, the triplet energy of the dopant is smaller than the triplet energy of the host, which is the delayed fluorescent compound of the present invention.

In addition, the light emitting material layer 123 includes the delayed fluorescent compound of the present invention as a first dopant material and further includes a host material and a second dopant material, and the sum of the doped first and second dopant materials is The host material is doped in an amount of about 1 to 30 wt%, thereby emitting blue light. Since the light emitting material layer 123 includes a host material and first and second dopant materials, luminous efficiency and color are further improved.

In this case, the triplet energy of the first dopant, which is the delayed fluorescent compound of the present invention, is smaller than the triplet energy of the host and greater than the triplet energy of the second dopant. Further, in this case, the difference (ΔE _ST ) between the singlet energy of the first dopant and the triplet energy of the first dopant is 0.3 eV or less. As ΔE _ST is smaller, the luminous efficiency increases, and even if the difference (ΔE _ST ) between the singlet energy and the triplet energy of the first dopant, which is the delayed fluorescent compound of the present invention, becomes about 0.3 eV, which is relatively large, the singlet state ( S ₁ ) Exciton and triplet state (T ₁ ) An exciton can be transitioned to an intermediate state (I ₁ ). (ΔE _ST ≤0.3)

As described above, the delayed fluorescent compound of the present invention contains both an electron donor moiety and an electron acceptor moiety and has strong electron accepting properties of benzo[4,5]thieno[2] ,3-b] Since quinoxaline is used as an electron acceptor moiety, luminous efficiency is improved.

That is, a dipole is formed from the electron donor moiety to the electron acceptor moiety and the dipole moment inside the molecule is increased, so that the luminous efficiency is improved. This is greatly improved.

In addition, the dihedral angle between the electron acceptor moiety and the electron acceptor moiety increases, so that deep blue light is emitted.

Accordingly, the organic light emitting diode device including the delayed fluorescent compound of the present invention can improve luminous efficiency and realize high-quality images.

Although the above has been described with reference to the preferred embodiment of the present invention, those skilled in the art can variously modify and change the present invention within the scope without departing from the spirit and scope of the present invention described in the claims below. You will understand that it can be done.

110: first electrode 120: organic light emitting layer
121: hole injection layer 122: hole transport layer
123: light emitting material layer 124: electron transport layer
125: electron injection layer 130: second electrode
E: organic light emitting diode

Claims (13)

delete A delayed fluorescent compound represented by the following formula (1), wherein each of D1 and D2 is selected from the following formula (2), any one of m or n is 0, and the other one of m or n is 1 or 2.
[Formula 1]

[Formula 2]

(In Formula 2, each of R1 and R2 is independently selected from C1-C10 alkyl,

is the bonding position for Formula 1 above.)
3. The method of claim 2,
The delayed fluorescence compound is any one of the following compounds.

3. The method of claim 2,
The difference between the singlet energy and the triplet energy of the delayed fluorescent compound is 0.3 eV or less.
delete a first electrode;
a second electrode facing the first electrode;
an organic light emitting layer positioned between the first and second electrodes;
The organic light emitting layer,
An organic light emitting diode device comprising a delayed fluorescent compound represented by the following Chemical Formula 1, wherein each of D1 and D2 is selected from the following Chemical Formula 2, any one of m or n is 0, and the other of m or n is 1 or 2 .
[Formula 1]

[Formula 2]

(In Formula 2, each of R1 and R2 is independently selected from C1-C10 alkyl,

is the bonding position for Formula 1 above.)
7. The method of claim 6,
The delayed fluorescent compound is an organic light emitting diode device of any one of the following compounds.

7. The method of claim 6,
The difference between singlet energy and triplet energy of the delayed fluorescent compound is 0.3 eV or less.
7. The method of claim 6,
The delayed fluorescent compound is used as a dopant, and the organic light emitting layer further comprises a host.
10. The method of claim 9,
The difference between the highest occupied molecular orbital level of the host (HOMO _Host ) and the highest occupied molecular orbital level (HOMO _Dopant ) of the dopant (|HOMO _Host -HOMO _Dopant |) or the lowest unoccupied molecular orbital level of the host (LUMO) _Host ) and the lowest unoccupied molecular orbital level (LUMO _Dopant ) of the dopant (|LUMO _Host -LUMO _Dopant |) is 0.5 eV or less.
7. The method of claim 6,
The delayed fluorescent compound is used as a host, and the organic light emitting layer further comprises a dopant.
7. The method of claim 6,
The delayed fluorescent compound is used as a first dopant, and the organic emission layer further includes a host and a second dopant,
The first triplet energy of the first dopant is smaller than the second triplet energy of the host and greater than the third triplet energy of the second dopant.
a substrate;
The organic light emitting diode device of any one of claims 6 to 12 positioned on the substrate;
an encapsulation film covering the organic light emitting diode device;
and a cover window on the encapsulation film.

Images