CN105176520B - One kind is based on 4,4′The preparation and application of the luminous and material of main part of substitution benzil core - Google Patents

Abstract

The invention belongs to the technical field of organic photoelectric materials, and discloses the preparation and application of a luminescent and host material based on a 4,4'-substituted benzil nucleus. The luminescent material of the present invention is prepared by using 4,4'-dibromobenzil as a starting material and through Buchwald-Hartwig coupling reaction under the protection of nitrogen. The luminescent material of the present invention uses 4,4'-substituted benzil as the main structure, and by changing the connection mode of the donor, the molecular weight, π conjugation and electrophilicity, charge transport ability and light color of the material can be adjusted, and It can effectively solve the problem of carrier imbalance of unipolar light-emitting materials. Its application in organic light emitting diodes can greatly improve the external quantum efficiency of traditional fluorescent organic light emitting diode devices.

Description

Preparation and preparation of a luminescent and host material based on 4,4'-substituted benzil nucleus application

technical field

The invention belongs to the technical field of organic photoelectric materials, and specifically relates to the preparation and application of a luminescent and host material based on a 4,4'-substituted benzil nucleus.

Background technique

In order to improve the efficiency of organic photoelectric devices, compared with polymer materials, small molecule materials can obtain higher device efficiency due to their definite structure and convenient purification, so that they may be commercially applied. However, the efficiency of devices based on traditional organic fluorescent materials is greatly limited because only 25% of the singlet excitons can be utilized. Recently, the Japanese Adachi research group used the mechanism of thermally activated delayed fluorescence, and the exciton utilization rate of all organic materials can also reach 100%, making the device efficiency of organic fluorescence leap forward. However, due to the variety of such materials, it is of great significance to expand the types of such materials for future application choices. Based on this mechanism, the small molecule red, green and blue three-color light-emitting materials and the preparation of flexible devices have incomparable advantages for reducing the cost of materials and commercial applications, so the development and research of new materials is particularly important.

So far, there have been some reports on organic light-emitting small molecules with 4,4'-substituted benzil as the core, but a lot of work has focused on using it as an organic reaction intermediate, and its potential in organic light-emitting diodes remains to be explored. At the same time, there is no related report on using thermally excited delayed fluorescent materials as sensitizing hosts for solution processing.

So far, organic light-emitting diodes have made great progress, but so far, organic small molecule light-emitting materials with simple structure, good performance and meeting commercial needs are still very limited, and low-cost and high-efficiency light-emitting materials are still of great importance. meaning.

Contents of the invention

In order to solve the above shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a luminescent and host material based on 4,4'-substituted benzil nucleus.

Another object of the present invention is to provide a method for preparing the above-mentioned luminescent and host material based on 4,4'-substituted benzil nucleus.

Another object of the present invention is to provide the above-mentioned luminescent and host materials based on 4,4'-substituted benzil nucleus for application in organic electroluminescent devices.

The object of the invention is achieved through the following technical solutions:

A luminescent and host material based on a 4,4'-substituted benzil nucleus, the molecular structure of the luminescent and host material is shown in the following formula:

Wherein Ar is the arylamino group of the structural formula shown in any one of (1)～(17):

Preferably, the luminescent material has the molecular structural formula shown in any one of the following P1-P17:

The above-mentioned preparation method of luminescent and host materials based on 4,4'-substituted benzil nucleus, said preparation method refers to the intermediate with the structure shown in formula (a) through Buchwald-Hartwig coupling reaction under the protection of nitrogen gas Prepared to get,

Formula (a).

Application of the above-mentioned luminescence based on 4,4'-substituted benzil nucleus and host material in an organic electroluminescence device, the organic electroluminescence device comprises a substrate, and an anode layer sequentially formed on the substrate, at least one light emitting Layer unit and cathode layer; the light-emitting layer unit includes a hole injection layer, a hole transport layer, at least one light-emitting layer and an electron transport layer; the light-emitting layer contains at least one of the above-mentioned 4,4'-substituted benzene-based Luminescent and host materials for diacyl nuclei.

Preferably, the light emitting layer refers to a red light emitting layer or a yellow light emitting layer.

The principle of the present invention is: the luminescent and host material with 4,4'-substituted benzil structure, the benzil group has a strong electron-withdrawing ability, which helps to obtain a strong charge transfer state compound, thereby obtaining a thermal Activates delayed fluorescent compounds.

The preparation method of the present invention and the resulting product have the following advantages and beneficial effects:

(1) The present invention uses commercially available 4,4'-dibromobenzil as the initial reaction raw material, and obtains the final product through a simple one-step reaction, thus providing the possibility for industrial application;

(2) The material of the present invention is simple to synthesize, has a single structure, and has a definite molecular weight; it has a relatively high decomposition temperature and a relatively low sublimation temperature, and can be easily sublimated into a high-purity luminescent material or used as a host material;

(3) By changing the connection mode of the donor, the material of the present invention can adjust the molecular weight, π conjugation, electrophilicity, charge transport ability and light color of the material, and can effectively solve the problem of unipolar luminescent material carrier the problem of imbalance;

(4) The material of the present invention has good solubility, which provides the possibility of solution processing, thereby simplifying the device manufacturing process;

(5) The material of the present invention can be applied to organic light emitting diodes, and can greatly improve the external quantum efficiency of traditional fluorescent organic light emitting diode devices.

Description of drawings

1 to 3 are respectively the current density-voltage-brightness curve, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in Example 18;

4 to 6 are respectively the current density-voltage-brightness curve, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in Example 19;

7 to 9 are respectively the current density-voltage-brightness curve, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in Example 20;

10 to 12 are respectively the current density-voltage-brightness curve, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in Example 21;

13 to 15 are respectively the current density-voltage-brightness curve, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in Example 22.

detailed description

The present invention will be further described in detail below in conjunction with the embodiments and the accompanying drawings, but the embodiments of the present invention are not limited thereto.

Example 1

In this example, the luminescent and host material P1 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

Specific implementation steps: add 4,4'-dibromo-substituted benzil (0.368mg, 1mmol) and carbazole (367.4mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene in a 250ml three-necked flask, Palladium acetate (44mg, 0.2mmol) was added under nitrogen protection, and then tri-tertbutylphosphine (0.73ml, 0.73mmol) was added dropwise thereto. Under the protection of nitrogen, the reaction was heated to reflux for 12h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate and passed through a silica gel column to obtain 500 mg of a yellow solid (90% yield). Molecular formula: C ₃₈ H ₂₄ N ₂ O ₂ ; molecular weight: 540.62; elemental analysis: C, 84.42; H, 4.47; N, 5.18; O, 5.92.

Example 2

In this example, the luminescent and host material P2 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

Specific implementation steps: in a 250ml three-necked flask, add 4,4'-dibromo-substituted benzil (0.368mg, 1mmol) and tert-butylcarbazole (614mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene , palladium acetate (44mg, 0.2mmol) was added under nitrogen protection, and then tri-tertbutylphosphine (0.73ml, 0.73mmol) was added dropwise thereto. Under the protection of nitrogen, the reaction was heated to reflux for 12h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, and passed through a silica gel column to obtain 700 mg of a yellow solid (91.5% yield). Molecular formula: C ₅₄ H ₅₆ N ₂ O ₂ ; Molecular weight: 765.05; Elemental analysis: C, 84.78; H, 7.38; N, 3.66; ), 8.14 (t, J=1.2Hz, 4H), 7.83–7.79 (m, 4H), 7.52–7.46 (m, 8H), 1.51–1.43 (m, 36H).

Example 3

In this example, the luminescent and host material P3 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

Specific implementation steps: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol), p-carbazole to a 250ml flask Phenylboronate (811mg, 2.2mmol), and then 200mg of triphenylphosphopalladium catalyst was added, and the mixture was refluxed at 110°C for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated 600 mg of yellow solid with a yield of 86.7%. Molecular formula: C ₅₀ H ₃₂ N ₂ O ₂ ; molecular weight: 692.82; elemental analysis: C, 86.68; H, 4.66; N, 4.04; O, 4.62.

Example 4

In this example, the luminescent and host material P4 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

The specific implementation steps are: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol) into a 250ml flask, p-tert Butylcarbazole phenyl borate (1.06g, 2.2mmol), and then 200mg of triphenylphosphopalladium catalyst was added, and refluxed at 110°C for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated 850 mg of yellow solid with a yield of 92.7%. Molecular formula: C ₆₆ H ₆₄ N ₂ O ₂ ; molecular weight: 917.25; elemental analysis: C, 86.42; H, 7.03; N, 3.05; O, 3.49.

Example 5

In this example, the luminescent and host material P5 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

The specific implementation steps are: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol) into a 250ml flask, p-tert Butylcarbazole phenyl borate (811mg, 2.2mmol), and then 200mg of triphenylphosphopalladium catalyst was added, and refluxed at 110°C for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated 599 mg of a yellow solid with a yield of 86.7%. Molecular formula: C ₅₀ H ₃₂ N ₂ O ₂ ; molecular weight: 692.82; elemental analysis: C, 86.68; H, 4.66; N, 4.04; O, 4.62.

Example 6

In this example, the luminescent and host material P6 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

The specific implementation steps are: add 4,4'-dibromo-substituted benzil (0.368mg, 1mmol) and diphenylamine (614mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene in a 250ml three-necked flask, Palladium acetate (44mg, 0.2mmol) was added under nitrogen protection, and then tri-tertbutylphosphine (0.73ml, 0.73mmol) was added dropwise thereto. Under the protection of nitrogen, the reaction was heated to reflux for 12h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, and passed through a silica gel column to obtain 700 mg of a yellow solid (91.5% yield). Molecular formula: C ₃₈ H ₂₈ N ₂ O ₂ ; molecular weight: 544.65; elemental analysis: C, 83.80; H, 5.18; N, 5.14; O, 5.87.

Example 7

In this example, the luminescent and host material P7 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

Specific implementation steps: add 4,4'-dibromo-substituted benzil (0.368mg, 1mmol) and tert-butyldiphenylamine (614mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene in a 250ml three-necked flask , palladium acetate (44mg, 0.2mmol) was added under nitrogen protection, and then tri-tertbutylphosphine (0.73ml, 0.73mmol) was added dropwise thereto. Under the protection of nitrogen, the reaction was heated to reflux for 12h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, and passed through a silica gel column to obtain 700 mg of an orange solid (yield 92%). Molecular formula: C ₅₄ H ₆₀ N ₂ O ₂ ; molecular weight: 769.09; elemental analysis: C, 84.33; H, 7.86; N, 3.64; O, 4.16.

Example 8

In this example, the luminescent and host material P8 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

Specific implementation steps: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol), p-diphenylamine into a 250ml flask Phenylboronate (811mg, 2.2mmol), and then 200mg of triphenylphosphopalladium catalyst was added, and the mixture was refluxed at 110°C for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated 600 mg of yellow solid with a yield of 86.7%. Molecular formula: C ₅₀ H ₃₆ N ₂ O ₂ ; molecular weight: 696.85; elemental analysis: C, 86.18; H, 5.21; N, 4.02; O, 4.59.

Example 9

In this example, the luminescent and host material P9 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

Specific implementation steps: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol), p-carbazole to a 250ml flask Phenylboronate (811mg, 2.2mmol), and then 200mg of triphenylphosphopalladium catalyst was added, and the mixture was refluxed at 110°C for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated 600 mg of yellow solid with a yield of 86.7%. Molecular formula: C ₆₆ H ₆₈ N ₂ O ₂ ; molecular weight: 921.28; elemental analysis: C, 86.05; H, 7.44; N, 3.04; O, 3.47.

Example 10

In this example, the luminescent and host material P10 based on 4,4'-substituted benzil nucleus is prepared, and its reaction is shown in the following formula:

Specific implementation steps: add 4,4'-dibromo-substituted benzil (0.368mg, 1mmol) and dimethylacridine (460mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene in a 250ml three-necked flask , palladium acetate (44mg, 0.2mmol) was added under nitrogen protection, and then tri-tertbutylphosphine (0.73ml, 0.73mmol) was added dropwise thereto. Under the protection of nitrogen, the reaction was heated to reflux for 12h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate and passed through a silica gel column to obtain 500 mg of an orange solid (yield 80%). Molecular formula: C ₄₄ H ₃₆ N ₂ O ₂ ; Molecular weight: 624.78; Elemental analysis: C, 84.59; H, 5.81; N, 4.48; ), 7.57–7.51 (m, 4H), 7.48 (dt, J=11.1, 5.4 Hz, 4H), 7.08–6.97 (m, 8H), 6.52–6.44 (m, 4H). 1.65 (s, 12H).

Example 11

This example prepares the luminescent and host material P11 based on 4,4'-substituted benzil nucleus, and its reaction is shown in the following formula:

The specific implementation steps are: add 4,4'-dibromo-substituted benzil (0.368mg, 1mmol) and phenoxazine (403mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene in a 250ml three-necked flask , palladium acetate (44mg, 0.2mmol) was added under nitrogen protection, and then tri-tertbutylphosphine (0.73ml, 0.73mmol) was added dropwise thereto. Under the protection of nitrogen, the reaction was heated to reflux for 12h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate and passed through a silica gel column to obtain 530 mg of a red solid (yield 75%). Molecular formula: C ₃₈ H ₂₄ N ₂ O ₄ ; molecular weight: 572.62; elemental analysis: C, 79.71; H, 4.22; N, 4.89; O, 11.18. 1H NMR (500MHz, CDCl3) δ8.25 (d, J = 8.0 Hz, 4H), 7.57(d, J=8.1Hz, 4H), 6.74(dd, J=14.9, 7.2Hz, 8H), 6.64(t, J=7.2Hz, 4H), 6.05(d, J=7.7 Hz, 4H).

Example 12

In this example, the luminescent and host material P12 based on the 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

The specific implementation steps are: add 4,4'-dibromo-substituted benzil (0.368mg, 1mmol) and phenothiazine (438mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene in a 250ml three-necked flask , palladium acetate (44mg, 0.2mmol) was added under nitrogen protection, and then tri-tertbutylphosphine (0.73ml, 0.73mmol) was added dropwise thereto. Under the protection of nitrogen, the reaction was heated to reflux for 12h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, and passed through a silica gel column to obtain 560 mg of a yellow solid (92.7% yield). Molecular formula: C ₃₈ H ₂₄ N ₂ O ₂ S ₂ ; molecular weight: 604.74; elemental analysis: C,75.47; H,4.00; N,4.63; O,5.29; S,10.60. 1H NMR (500MHz, CDCl3) δ7.80 (d,J=9.0Hz,4H),7.45–7.41(m,4H),7.33–7.27(m,8H),7.19(t,J=5.9Hz,4H),7.06(t,J=8.9Hz, 4H).

Example 13

In this example, the luminescent and host material P13 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

Specific implementation steps: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol), p-phenyl Phenazine phenylboronate (1.01 g, 2.2 mmol) was then added with 200 mg of triphenylphosphopalladium catalyst and refluxed at 110° C. for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated to obtain 600 mg of orange-red solid with a yield of 68.6%. Molecular formula: C ₆₂ H ₄₂ N ₄ O ₂ ; molecular weight: 875.04; elemental analysis: C, 85.10; H, 4.84; N, 6.40; O, 3.66.

Example 14

This example prepares the luminescent and host material P14 based on 4,4'-substituted benzil nucleus, and its reaction is shown in the following formula:

Specific implementation steps: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol), dimethyl Acridine phenyl borate (905mg, 2.2mmol), and then 200mg of triphenylphosphopalladium catalyst was added, and the mixture was refluxed at 110°C for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated to obtain 600 mg of orange-red solid with a yield of 77.2%. Molecular formula: C ₅₆ H ₄₄ N ₂ O ₂ ; molecular weight: 776.98; elemental analysis: C, 86.57; H, 5.71; N, 3.61; O, 4.12.

Example 15

In this example, the luminescent and host material P15 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

Specific implementation steps: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol), dimethyl Acridine phenyl borate (845mg, 2.2mmol), and then add 200mg of triphenylphosphopalladium catalyst, and reflux at 110°C for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated 550 mg of a red solid with a yield of 75.9%. Molecular formula: C ₅₀ H ₃₂ N ₂ O ₄ ; Molecular weight: 724.82; Elemental analysis: C, 82.86; H, 4.45; N, 3.86; O, 8.83.

Example 16

This example prepares the luminescent and host material P16 based on 4,4'-substituted benzil nucleus, and its reaction is shown in the following formula:

Specific implementation steps: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol), phenothiazine into a 250ml flask Phenylboronate (888mg, 2.2mmol), and then 200mg of triphenylphosphopalladium catalyst was added, and the mixture was refluxed at 110°C for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated 610 mg of orange-red solid with a yield of 80.7%. Molecular formula: C ₅₀ H ₃₂ N ₂ O ₂ S ₂ ; Molecular weight: 756.94; Elemental analysis: C, 79.34; H, 4.26; N, 3.70; O, 4.23; S, 8.47.

Example 17

In this example, the luminescent and host material P17 based on 4,4'-substituted benzil nucleus is prepared, and the reaction is shown in the following formula:

Specific implementation steps: under a nitrogen atmosphere, add 100ml of toluene, 30ml of absolute ethanol, 40ml of 2M potassium carbonate aqueous solution, 4,4'-dibromo-substituted benzil (0.368mg, 1mmol), phenothiazine into a 250ml flask Phenylboronate (1.01 g, 2.2 mmol), and then 200 mg of triphenylphosphopalladium catalyst was added, and refluxed at 110° C. for 12 hours. Cool to room temperature, extract with dichloromethane, and dry over anhydrous magnesium sulfate. Column chromatography separated 610 mg of orange-red solid with a yield of 80.7%. Molecular formula: C ₆₂ H ₄₂ N ₄ O ₂ ; molecular weight: 875.04; elemental analysis: C, 85.10; H, 4.84; N, 6.40; O, 3.66.

Example 18

An organic light emitting diode according to this embodiment has a device structure as follows:

ITO(125nm)/PEDOT:PSS(40)/1wt%DBP:15wt%

P2:CBP(40nm)/TmPyPB(50nm)/LiF(1nm)/Al(100nm)

The specific implementation steps are:

ITO transparent conductive glass is ultrasonically treated in a cleaning agent, then cleaned with deionized water, ultrasonically degreased in acetone: ethanol mixed solvent, baked in a clean environment until the water is completely removed, cleaned with ultraviolet light and ozone, and cleaned with ion bombardment.

A 40 nm thick PEDOT:PSS was spin-coated at 3000 rpm on a pretreated clean ITO glass substrate and dried at 200 °C for 10 min. Subsequently, DBP, P2 and CBP were blended and dissolved in chlorobenzene at a mass percentage of 1:15:84, and a 40 nm thick light-emitting layer was spin-coated at a speed of 1500 rpm, and the film was then annealed under nitrogen for 10 min. Finally, TmPyPB and LiF/Al were thermally deposited on the light-emitting layer by evaporation.

The current density-voltage-brightness curve, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in this embodiment are shown in Figure 1, Figure 2 and Figure 3, respectively.

Example 19

An organic light emitting diode according to this embodiment has a device structure as follows:

ITO(125nm)/PEDOT:PSS(40nm)/1wt%DBP:99wt%P2

(40nm)/TmPyPB(50)/LiF(1nm)/Al(100nm)

The specific implementation steps are:

ITO transparent conductive glass is ultrasonically treated in a cleaning agent, then cleaned with deionized water, ultrasonically degreased in acetone: ethanol mixed solvent, baked in a clean environment until the water is completely removed, cleaned with ultraviolet light and ozone, and cleaned with ion bombardment.

A 40 nm thick PEDOT:PSS was spin-coated at 3000 rpm on a pretreated clean ITO glass substrate and dried at 200 °C for 10 min. Then DBP and P2 were blended and dissolved in chlorobenzene at a mass percentage of 1:99, and a luminescent layer with a thickness of 40 nm was spin-coated at a speed of 1500 rpm. The film was then annealed under nitrogen for 10 min. Finally, TmPyPB and LiF/Al were thermally deposited on the light-emitting layer by evaporation.

The current density-voltage-brightness curve, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in this embodiment are shown in Figure 4, Figure 5 and Figure 6, respectively.

Example 20

An organic light emitting diode according to this embodiment has a device structure as follows:

ITO(125nm)/PEDOT:PSS(40nm)/1wt%DBP:99wt%P10

(40nm)/TmPyPB(50nm)/LiF(1nm)/Al(100nm)

The specific implementation steps are:

ITO transparent conductive glass is ultrasonically treated in a cleaning agent, then cleaned with deionized water, ultrasonically degreased in acetone: ethanol mixed solvent, baked in a clean environment until the water is completely removed, cleaned with ultraviolet light and ozone, and cleaned with ion bombardment.

A 40 nm thick PEDOT:PSS was spin-coated at 3000 rpm on a pretreated clean ITO glass substrate and dried at 200 °C for 10 min. Then DBP and P10 were blended and dissolved in chlorobenzene at a mass ratio of 1:99, and a luminescent layer with a thickness of 40 nm was spin-coated at a speed of 1500 rpm. The film was then annealed under nitrogen for 10 min. Finally, TmPyPB and LiF/Al were thermally deposited on the light-emitting layer by evaporation.

The current density-voltage-brightness curve, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in this embodiment are shown in Figure 7, Figure 8 and Figure 9, respectively.

Example 21

An organic light emitting diode according to this embodiment has a device structure as follows:

ITO(125nm)/PEDOT:PSS(40nm)/1wt%DBP:5%P10:94wt%CBP

(40nm)/TmPyPB(50nm)/LiF(1nm)/Al(100nm)

The specific implementation steps are:

ITO transparent conductive glass is ultrasonically treated in a cleaning agent, then cleaned with deionized water, ultrasonically degreased in acetone: ethanol mixed solvent, baked in a clean environment until the water is completely removed, cleaned with ultraviolet light and ozone, and cleaned with ion bombardment.

A 40 nm thick PEDOT:PSS was spin-coated at 3000 rpm on a pretreated clean ITO glass substrate and dried at 200 °C for 10 min. Then DBP, P10 and CBP were blended and dissolved in chlorobenzene at a mass percentage of 1:5:94, and a luminescent layer with a thickness of 40 nm was spin-coated at a speed of 1500 rpm. The film was then annealed under nitrogen for 10 min. Finally, TmPyPB and LiF/Al were thermally deposited on the light-emitting layer by evaporation.

The current density-voltage-brightness graph, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in this embodiment are shown in Figure 10, Figure 11 and Figure 12, respectively.

Example 22

An organic light emitting diode according to this embodiment has a device structure as follows:

ITO(125nm)/PEDOT:PSS(40nm)/15%P2:85wt%CBP

(40nm)/TmPyPB(50nm)/LiF(1nm)/Al(100nm)

The specific implementation steps are:

ITO transparent conductive glass is ultrasonically treated in a cleaning agent, then cleaned with deionized water, ultrasonically degreased in acetone: ethanol mixed solvent, baked in a clean environment until the water is completely removed, cleaned with ultraviolet light and ozone, and cleaned with ion bombardment.

A 40 nm thick PEDOT:PSS was spin-coated at 3000 rpm on a pretreated clean ITO glass substrate and dried at 200 °C for 10 min. Subsequently, P2 and CBP were blended and dissolved in chlorobenzene at a mass percentage of 15:85, and a luminescent layer with a thickness of 40 nm was spin-coated at a speed of 1500 rpm. The film was then annealed under nitrogen for 10 min. Finally, TmPyPB and LiF/Al were thermally deposited on the light-emitting layer by evaporation.

The current density-voltage-brightness graph, lumen efficiency-brightness-power efficiency graph and electroluminescence spectrum graph of the organic light emitting diode device obtained in this embodiment are shown in Figure 13, Figure 14 and Figure 15, respectively.

The molecular structural formula of the material used in the above embodiments is as follows:

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (2)

1. Application of a luminescent and host material based on 4,4'-substituted benzil nucleus in an organic electroluminescent device, the organic electroluminescent device comprising a substrate, and an anode layer sequentially formed on the substrate, At least one light-emitting layer unit and a cathode layer; the light-emitting layer unit includes a hole injection layer, a hole transport layer, at least one light-emitting layer and an electron transport layer; it is characterized in that: the light-emitting layer contains at least one based on 4 , luminescent and host materials of 4'-substituted benzil nuclei; the luminescent and host materials based on 4,4'-substituted benzil nuclei have the molecular structural formula shown in any one of the following P1-P17: 2. The application of a luminescent and host material based on 4,4'-substituted benzil nucleus in organic electroluminescent devices according to claim 1, characterized in that: the luminescent layer refers to red light Light emitting layer or yellow light emitting layer.