Organic light-emitting device and illumination or display device comprising same

Abstract

The invention relates to the technical field of preparation of organic photoelectric materials, in particular to an organic light-emitting device and a lighting or display device comprising the organic light-emitting device. In the invention, the boron-nitrogen compound with triphenylsilyl matched with carbazole and alkyl is used as a light-emitting doping material, and a defined triarylamine compound is used as a light-emitting auxiliary material, so that the light-emitting efficiency of the organic light-emitting device can be effectively improved, and the organic light-emitting device has a very good application prospect.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic material preparation technology, specifically to an organic electroluminescent device and a lighting or display device containing the device. Background Technology

[0002] Organic light-emitting diodes (OLEDs), also known as organic light-emitting devices, are a technology that converts electrical energy into light energy through organic light-emitting materials. This technology involves applying voltage to an organic light-emitting element to inject holes from the anode and electrons from the cathode into the light-emitting layer. The injected holes and electrons then recombine to form excitons, causing light to be emitted.

[0003] Existing luminescent materials still have shortcomings in improving device performance. Even with the combination of multiple materials, display technology still suffers from high driving voltage and short display lifespan, severely hindering its further practical application. Existing boron-nitrogen luminescent doped materials still have room for improvement in terms of operating lifespan and luminous efficiency in device applications.

[0004] Therefore, continuous efforts are needed to develop organic light-emitting devices with low voltage drive, high brightness, and long lifespan to solve the above problems. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides an organic electroluminescent device and a display or lighting apparatus containing the device. In the provided organic electroluminescent device, through iterative improvements to the luminescent doping material, a luminescent doping material is obtained by using a combination of triarylsilyl groups, carbazole, and alkyl groups as key groups on the boron-nitrogen core structure. Combined with specific luminescent auxiliary materials, the device exhibits higher luminescence and operational lifespan, with a particularly significant improvement in lifespan.

[0006] This invention provides an organic electroluminescent device, which is achieved through the following technical solution: An organic electroluminescent device, comprising: Substrate layer; A first electrode is placed on the substrate; An organic light-emitting functional layer is disposed on the first electrode; The second electrode is located on the organic light-emitting functional layer. The organic light-emitting functional layer includes a light-emitting layer, which comprises a doped material of formula I: ; In Formula I, X1 is selected from O or S; R1 and R2 each independently represent monosubstituted, disubstituted, or polysubstituted substances; R1, R2, R3, and R4 each independently represent hydrogen, deuterium, C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C5-C36 heteroaryl; the substituted or unsubstituted substances are selected from one or more of hydrogen, deuterium, C1-C12 alkyl, and C3-C24 cycloalkyl; "D" represents deuterium, and n is an integer from 0 to 15; The organic light-emitting functional layer further includes a light-emitting auxiliary layer, wherein the light-emitting auxiliary layer is a material with a structure of Formula II: ; Wherein, L, L1, and L2 are each independently selected from single bonds and C6-C30 arylene groups, and X is selected from O or S atoms; Ar1 ​​and Ar2 are each independently selected from deuterated or undeuterated C6-C30 aryl groups and deuterated or undeuterated C5-C36 heteroaryl groups; Ra and Rb are each independently selected from hydrogen, deuterium, and phenyl, and at least one of Ra and Rb is selected from phenyl; n1 is selected from integers from 0 to 3, and n2 is selected from integers from 0 to 4.

[0007] Preferably, the hydrogen atoms in Formula I and Formula II may be partially or completely deuterated.

[0008] Preferably, in Formula II, when Ra and Rb are selected from phenyl groups, the phenyl groups are connected by single bonds or fusion.

[0009] Preferably, in Formula I, R1 and R2 are each independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, C1-C4 alkyl-substituted or unsubstituted carbazole groups each time they appear; and at least one of them is selected from C1-C4 alkyl-substituted or unsubstituted carbazole groups.

[0010] Preferably, in Formula I, R1 is disubstituted or polysubstituted, and each time R1 appears, it is independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, C1-C4 alkyl-substituted or unsubstituted carbazolyl, and one of them is C1-C4 alkyl-substituted or unsubstituted carbazolyl; R2 is monosubstituted, disubstituted or polysubstituted, and each time R2 appears, it is selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, or other substituted groups, either the same or different.

[0011] Preferably, in Formula I, R3 and R4 are each independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, phenyl, tert-butylphenyl, and tetramethyltetrahydronaphthyl.

[0012] More preferably, in Formula I, R3 is selected from tert-butyl, phenyl, tert-butylphenyl, and tetramethyltetrahydronaphthyl.

[0013] More preferably, in Formula I, R4 is selected from hydrogen, deuterium, deuterated or undeuterated methyl, deuterated or undeuterated tert-butyl.

[0014] More preferably, in Formula I, "D" represents deuterium, and n is an integer of 0 or 15.

[0015] According to one or more embodiments, the present invention provides an organic electroluminescent device, wherein the doping material in the light-emitting layer is selected from any one of the following chemical structures, wherein tBu represents tert-butyl and D represents deuterium: .

[0016] Preferably, in Formula II, L1 and L2 are each independently selected from single bonds, phenylene, and naphthylene; Ar1 ​​and Ar2 are selected from the following groups, either deuterated or undeuterated: phenyl, naphthyl, phenyl-substituted naphthyl, and dibenzofuranyl.

[0017] Preferably, in Formula II, L is selected from phenylene or biphenylene.

[0018] According to one or more embodiments, the present invention provides an organic electroluminescent device, wherein the compound of the light-emitting auxiliary layer is selected from any one or more of the following chemical structures, wherein D represents deuterium: .

[0019] The organic electroluminescent device of the present invention can be used in OLED lighting or display devices.

[0020] The present invention also provides a display or lighting device comprising one or more of the organic electroluminescent devices described above.

[0021] The present invention also provides a composition comprising a compound of formula I: ; In Formula I, X1 is selected from O or S; R1 and R2 each independently represent monosubstituted, disubstituted, or polysubstituted substances; R1, R2, R3, and R4 each independently represent hydrogen, deuterium, C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C5-C36 heteroaryl; the substituted or unsubstituted substances are selected from one or more of hydrogen, deuterium, C1-C12 alkyl, and C3-C24 cycloalkyl; "D" represents deuterium, and n is an integer from 0 to 15; And materials including those with a Formula II structure: ; Wherein, L, L1, and L2 are each independently selected from single bonds and C6-C30 arylene groups, and X is selected from O or S atoms; Ar1 ​​and Ar2 are each independently selected from deuterated or undeuterated C6-C30 aryl groups and deuterated or undeuterated C5-C36 heteroaryl groups; Ra and Rb are each independently selected from hydrogen, deuterium, and phenyl; and at least one of Ra and Rb is selected from phenyl; n1 is selected from integers from 0 to 3, and n2 is selected from integers from 0 to 4.

[0022] Preferably, in Formula II, when Ra and Rb are selected from phenyl groups, the phenyl groups are connected by single bonds or fusion.

[0023] Preferably, the hydrogen atoms in Formula I and Formula II may be partially or completely deuterated.

[0024] In summary, compared with the prior art, the present invention has the following beneficial effects: In the organic electroluminescent device of the present invention, a light-emitting doped material is obtained by defining the combination of aromatic silanes with carbazole and alkyl groups as key groups on the boron-nitrogen core structure. When applied in an organic light-emitting device with defined light-emitting auxiliary materials, the luminous efficiency and working life of the organic light-emitting device can be effectively improved. Detailed Implementation The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0025] The aromatic derivatives described in this invention refer to divalent groups formed by removing two hydrogen atoms from an aryl group (such as benzene, naphthalene, anthracene, etc.). They can include monocyclic, fused-ring, or polycyclic structures and may contain substituents. Common types include phenylene, biphenylene, and naphthylene, but are not limited to these.

[0026] Aryl or aromatic group – as used herein, both non-fused and fused systems are considered. The aryl group can be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4”-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-dimethylyl, 3,4-dimethylyl, 2,5-dimethylyl, mestriylyl, and m-tetraphenyl.

[0027] The term "heteroaryl" refers to a group obtained by replacing one or more aromatic carbon atoms in an aryl group with heteroatoms. These heteroatoms include, but are not limited to, oxygen, sulfur, silicon, or nitrogen atoms. The heteroaryl group can be a monocyclic or fused-ring heteroaryl group, and can have 5 to 36 carbon atoms, preferably 6 to 20 carbon atoms. Examples include carbazolyl, pyrrolel, pyridinyl, thiophenel, furanyl, indolyl, quinolinyl, isoquinolinyl, benzothiophenel, benzofuranyl, dibenzofuranyl, dibenzothiophenel, etc., but are not limited to these.

[0028] "Alkyl" includes both straight-chain and branched alkyl groups. Preferred alkyl groups are those containing 1-12 carbon atoms, including methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. Examples may include methyl, ethyl, propyl, and tert-butyl. Additionally, the alkyl group may optionally be substituted.

[0029] Throughout this specification, unless explicitly stated otherwise, the term "including" any component will be understood to imply the inclusion of other components, not to exclude any other components. Furthermore, it should be understood that throughout this specification, when an element such as a layer, film, region, or substrate is referred to as being "on" or "above" another element, it may be "directly on" the other element, or there may be intermediate elements present. Additionally, "on" or "above" means located above the target portion, and not necessarily above it in the direction of gravity.

[0030] One object of the present invention is to provide an organic light-emitting device (OLED) comprising: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; a second electrode on the organic light-emitting functional layer; the light-emitting layer comprising a light-emitting doping material of Formula I of the present invention; the organic light-emitting functional layer further comprising a light-emitting auxiliary layer, the light-emitting auxiliary layer containing a triarylamine structure of Formula II.

[0031] In a preferred embodiment of the present invention, an OLED is provided, comprising a substrate, an anode, an organic light-emitting functional layer, a cathode, and a capping layer. The organic light-emitting functional layer may include a light-emitting layer, a hole transport layer, a hole injection layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., or may only include a light-emitting layer and one or more other layers. The light-emitting layer comprises a doped material of Formula I. The light-emitting auxiliary layer comprises one or more components of compounds shown in Formula II above. Optionally, a protective layer and / or an encapsulation layer are further provided above the capping layer.

[0032] The substrate described in this invention can be any substrate typically used in organic light-emitting devices. It can be a glass or transparent plastic substrate, an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance, and their applications vary depending on their properties.

[0033] As the main material for the hole injection layer, hole transport layer, electron injection layer, hole transport layer, and light-emitting layer, any material can be selected from known materials used in OLED devices.

[0034] The present invention will now be described in detail with reference to specific embodiments. Unless otherwise specified, all raw materials and solvents used in the synthesis embodiments are commercially available, and the solvents were used directly without further processing.

[0035] Preparation Example Preparation Example 1

[0036] Synthesis method: 1) In a reaction flask, Zn (20.0 mmol) and 15 ml of N,N-dimethylacetamide were added. Then, under a nitrogen atmosphere, elemental iodine (0.5 mmol) was added, and the mixture was stirred for 10 min until the iodine color faded. CD3I (15.0 mmol) was then added. The reaction system was stirred at 25°C for 24 h, and then P-1 (10.0 mmol) and Pd(PPh3)Cl2 (0.2 mmol) were added simultaneously. The reaction system was heated to 30°C and stirred for 2 h, then cooled to 25°C. 150 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (3 × 50 ml). The collected organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was purified by silica gel chromatography using a dichloromethane:petroleum ether volume ratio of 1:2 to obtain the intermediate product P-2.

[0037] 2) Dissolve intermediates P-2 (1 mmol) and P-3 (1 mmol) in 5 ml of toluene solution. Then, under a nitrogen atmosphere, add sodium tert-butoxide (2 mmol), Pd2(dba)3 (0.01 mmol), and X-Phos (0.04 mmol). Reflux the reaction system for 12 h and then cool to 25 °C. Remove the solvent from the reaction system by rotary evaporation, and extract the residue with dichloromethane (3 × 100 ml). Wash the collected organic phase with water and dry with sodium sulfate. Remove the solvent by vacuum distillation, and purify the crude product by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:4) to obtain intermediate P-4.

[0038] 3) Dissolve intermediate product P-4 (1 mmol) and compound P-5 (1 mmol) in 5 ml of toluene solution. Under a nitrogen atmosphere, add sodium tert-butoxide (2 mmol), Pd2(dba)3 (0.01 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.04 mmol). Reflux the reaction system for 12 h and then cool to 25 °C. Remove the solvent from the reaction system by rotary evaporation, and extract the residue with dichloromethane (3 × 100 ml). Wash the collected organic phase with water and dry with sodium sulfate. Remove the solvent by vacuum distillation, and purify the crude product by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:8) to obtain intermediate product M1.

[0039] Preparation Example 2 Following the synthetic steps and reaction conditions of Preparation Example 1, intermediate product M2 was synthesized. The difference from Preparation Example 1 is that CD3I is replaced with tert-butyl iodine.

[0040] Preparation Example 3

[0041] Synthesis method: P3-1 (20 mmol) and P3-2 (21 mmol) were dissolved in 50 mL of toluene solution, and the reaction system was cooled to -30 °C. Under a nitrogen atmosphere, n-butyllithium (2.5 mol / L, 20 mmol) was added. The reaction system was then cooled to -30 °C. o The reaction was continued at C for 30 min, then the temperature was restored to 25 °C and stirred at 25 °C for 24 h. 5 ml of water was added to the reaction system and stirred for 30 min to quench the reaction. The solvent was then removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 ml). The collected organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was purified by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:8) to obtain intermediate product M3.

[0042] Preparation Example 4

[0043] Synthesis method: 1) Add P4-1 (20.0 mmol) and 200 ml dichloromethane to a reaction flask, start stirring, and cool the reaction solution to 0°C. Add N-bromosuccinimide (20.0 mmol) in four batches, and stir the reaction system at 0°C for 2 h. Remove the solvent by vacuum distillation, and purify the crude product by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:4) to obtain the intermediate product P4-2.

[0044] 2) Intermediates P4-2 (10 mmol) and P4-3 (10 mmol) were dissolved in 20 mL of o-dichlorobenzene solution. The reaction system was refluxed for 12 h under a nitrogen atmosphere and then cooled to 25 °C. The solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography using dichloromethane and petroleum ether (volume ratio = 1:4). The intermediate product P4-4 was obtained as the eluent.

[0045] 3) Intermediate product P4-4 (10 mmol) and compound P4-5 (10 mmol) were dissolved in 50 mL of toluene solution. Under a nitrogen atmosphere, sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.1 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.4 mmol) were added. The reaction system was refluxed for 12 h and then cooled to 25 °C. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The collected organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was purified by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:8). The intermediate product P4-6 was obtained as the eluent.

[0046] 4) Add intermediate P4-6 (10 mmol) to 40 mL of ethanol solution. Add hydrazine hydrate (15 mmol) under a nitrogen atmosphere. Reflux the reaction system for 4 h and then cool to 25 °C. Remove the solvent from the reaction system by rotary evaporation. The crude product is purified by silica gel chromatography using dichloromethane and petroleum ether (volume ratio = 1:4) to obtain intermediate product M4.

[0047] Preparation Example 5

[0048] Following the synthetic steps and reaction conditions of Preparation Example 4, intermediate product M5-1 or M5-2 was synthesized, the difference being that P4-5 was replaced with... or .

[0049] Preparation Example 6

[0050] Synthesis method: 1) Add Zn (60.0 mmol) and 45 ml N,N-dimethylacetamide to a reaction flask. Under a nitrogen atmosphere, add elemental iodine (1.5 mmol), stir for 10 min until the iodine color fades, then add CD3I (45.0 mmol). After stirring the reaction system at 25°C for 24 h, simultaneously add P6-1 (30.0 mmol) and Pd(PPh3)Cl2 (0.6 mmol). Heat the reaction system to 30°C and stir for 2 h, then cool to 25°C. Add 450 ml of water to the reaction system, extract with ethyl acetate (3 × 150 ml), wash the collected organic phase with water, and dry with sodium sulfate. Remove the solvent by vacuum distillation, and purify the crude product by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:2). The intermediate product is P6-2.

[0051] 2) Add P6-2 (20.0 mmol) and 200 ml of dichloromethane to the reaction flask, and cool the reaction solution to 0°C. Add N-bromosuccinimide (20.0 mmol) in four batches, and stir the reaction system at 0°C for 2 h. Remove the solvent from the reaction system by vacuum distillation, and purify the crude product by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:4). The intermediate product is P6-3.

[0052] 3) Intermediates P6-3 (10 mmol) and P6-4 (10 mmol) were dissolved in 20 mL of o-dichlorobenzene. The reaction system was refluxed for 12 h under a nitrogen atmosphere and then cooled to 25 °C. The solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography using dichloromethane and petroleum ether (volume ratio = 1:4). Intermediate product P6-5 was obtained.

[0053] 4) Dissolve intermediate P6-5 (10 mmol) and compound P6-6 (10 mmol) in 50 mL of toluene. Under a nitrogen atmosphere, add sodium tert-butoxide (15 mmol), Pd2(dba)3 (0.1 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.4 mmol). Reflux the reaction mixture for 12 h, then cool to 25 °C. Remove the solvent from the reaction mixture by rotary evaporation, and extract the residue with dichloromethane (3 × 100 mL). Wash the collected organic phase with water and dry with sodium sulfate. Remove the solvent by vacuum distillation, and purify the crude product by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:8). The intermediate product is P6-7.

[0054] 4) Add intermediate P6-7 (10 mmol) to 40 ml of ethanol. Add hydrazine hydrate (15 mmol) under a nitrogen atmosphere. Reflux the reaction system for 4 h and then cool to 25 °C. Remove the solvent from the reaction system by rotary evaporation. The crude product is purified by silica gel chromatography using dichloromethane and petroleum ether (volume ratio = 1:4) to obtain intermediate M6.

[0055] Preparation Example 7 Following the synthetic steps and reaction conditions of Preparation Example 6, intermediate product M7 was synthesized. The difference from Preparation Example 6 is that P6-6 is replaced with .

[0056] Preparation Example 8

[0057] Following the synthetic steps and reaction conditions of Preparation Example 4, intermediate product M8 was synthesized. The difference from Preparation Example 4 was that P4-1 was replaced with... Replace P4-5 with .

[0058] Example Example 1: Synthesis of Compound 1

[0059] Synthesis method: 1) In a three-necked reaction flask, SM1 (1 mmol) and SM2 (1 mmol) were dissolved in 50 mL of toluene solution. Under a nitrogen atmosphere, sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol) were added. The reaction system was refluxed for 72 h and then cooled to 25 °C. The solvent in the reaction system was removed by rotary evaporation. The residue was extracted with dichloromethane (3 × 100 mL), and the collected organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was purified by silica gel column chromatography. The eluent was dichloromethane:petroleum ether (volume ratio = 1:4). The intermediate product S1 was obtained.

[0060] 2) Dissolve intermediate product S1 (1 mmol) and SM3 (1 mmol) in 50 mL of toluene solution. Under a nitrogen atmosphere, add sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol). Reflux the reaction system for 72 h and then cool to 25 °C. Remove the solvent from the reaction system by rotary evaporation, and extract the residue with dichloromethane (3 × 100 mL). Wash the collected organic phase with water and dry with sodium sulfate. Remove the solvent by vacuum distillation, and purify the crude product by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:4). Intermediate product S2 is obtained.

[0061] 3) Intermediate product S2 (1 mmol) and M4 (1 mmol) obtained in Preparation Example 4 were dissolved in 50 ml of toluene solution. Sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol) were added under a nitrogen atmosphere. The reaction system was refluxed for 72 h and then cooled to 25 °C. The solvent in the reaction system was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 ml). The collected organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was purified by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:4). Intermediate product S3 was obtained.

[0062] 4) Dissolve intermediate S3 (1 mmol) and compound SM5 (1 mmol) in 5 ml xylene solution. Under a nitrogen atmosphere, add sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol). Reflux the reaction system for 72 h and then cool to 25 °C. Remove the solvent from the reaction system by rotary evaporation, and extract the residue with dichloromethane (3 × 100 ml). Wash the collected organic phase with water and dry with sodium sulfate. Remove the solvent by vacuum distillation, and purify the crude product by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:4). Intermediate product S4 is obtained.

[0063] 5) Add S4 (5 mmol) and DMF (150 ml) sequentially to the reaction flask; under nitrogen protection, cool to -10°C, dissolve N-bromosuccinimide (5 mmol) in DMF (50 ml), then add the NBS DMF solution to the flask, and stir overnight at 50°C in the dark. After the reaction is complete, cool and dilute the reaction solution with ethyl acetate, wash with saturated brine, concentrate, and slurry with ethyl acetate / petroleum ether, then wash with methanol to obtain S5.

[0064] 6) The intermediate S5 (1 mmol) was dissolved in 60 mL of anhydrous tert-butylbenzene. The reaction system was cooled to -78 °C, and n-BuLi (2 mmol, 2 mol / L in hexane) was slowly added. After reacting at -78 °C for 4 h, BBr3 (1 mmol) was slowly added. After reacting at -50 °C for 1 h, the temperature was raised to 25 °C, and N,N-diisopropylethylamine (3 mmol) was added. The mixture was heated to 120 °C and reacted for 12 h. After cooling to 25 °C, 5 mL of sodium acetate aqueous solution (1 mol / L) was added. The solvent in the reaction system was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The collected organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was purified by silica gel column chromatography using dichloromethane:petroleum ether (volume ratio = 1:8) to give the final product - compound 1.

[0065] Analysis by liquid chromatography-mass spectrometry yielded the following LC-MS (m / z) values: theoretical value 1350.67, measured value 1351.35.

[0066] Example 2: Synthesis of Compound 3 Following the synthesis steps and reaction conditions of Example 1, compound 3 was synthesized, differing from Example 1 in that SM2 was replaced with... The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1364.69, while the measured value was 1365.55.

[0067] Example 3: Synthesis of Compound 4 Following the synthesis steps and reaction conditions of Example 1, compound 4 was synthesized, the difference being that SM5 was replaced with... The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1364.69, while the measured value was 1365.51.

[0068] Example 4: Synthesis of Compound 6 Following the synthesis steps and reaction conditions of Example 1, compound 6 was synthesized. The difference from Example 1 is that SM5 was replaced with M2. The product was analyzed by liquid chromatography-mass spectrometry, and the LC-MS (m / z) values ​​were 1406.74 and 1407.56, respectively.

[0069] Example 5: Synthesis of Compound 7 Following the synthesis steps and reaction conditions of Example 1, compound 7 was synthesized. The difference from Example 1 is that SM1 was replaced with M3. The product was analyzed by liquid chromatography-mass spectrometry, and the LC-MS (m / z) values ​​were 1365.77 and 1366.53, respectively.

[0070] Example 6: Synthesis of Compound 8 Following the synthesis steps and reaction conditions of Example 1, compound 8 was synthesized. The difference from Example 1 is that SM1 was replaced with M3 and M4 was replaced with M6. The product was analyzed by liquid chromatography-mass spectrometry, and the LC-MS (m / z) values ​​were 1326.74 and 1327.58, respectively.

[0071] Example 7: Synthesis of Compound 9 Following the synthesis steps and reaction conditions of Example 1, compound 8 was synthesized. The difference from Example 1 is that SM1 was replaced with M3 and M4 was replaced with... The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1323.72, while the measured value was 1324.44.

[0072] Example 8: Synthesis of Compound 16 Following the synthesis steps and reaction conditions of Example 1, compound 16 was synthesized. The difference from the example is that SM1 was replaced with M3 and SM4 was replaced with M5-1. The product was analyzed by liquid chromatography-mass spectrometry, and the LC-MS (m / z) results were: theoretical value 1477.89, test value 1478.63.

[0073] Example 9: Synthesis of Compound 22 Following the synthesis steps and reaction conditions of Example 1, compound 22 was synthesized. The difference from the example was that SM1 was replaced with M3, and SM3 was replaced with... The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1381.75, while the measured value was 1382.51.

[0074] Example 10: Synthesis of Compound 23 Following the synthesis steps and reaction conditions of Example 1, compound 23 was synthesized. The difference from Example 1 was that SM1 was replaced with M3, and SM3 was replaced with... SM4 was replaced with M6, and the product was analyzed by liquid chromatography-mass spectrometry (LC-MS) with a theoretical value of 1342.72 and a measured value of 1343.54.

[0075] Example 11: Synthesis of Compound 34 Following the synthesis steps and reaction conditions of Example 1, compound 34 was synthesized, the difference being that SM3 was replaced with... The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1366.65, while the measured value was 1367.51.

[0076] Example 12: Synthesis of Compound 41 Following the synthesis steps and reaction conditions of Example 1, compound 41 was synthesized. The difference from Example 1 was that SM5 was replaced with M1, SM4 was replaced with M5-2, and SM2 was replaced with... The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1535.90, while the measured value was 1536.78.

[0077] Example 13: Synthesis of Compound 47 Following the synthesis steps and reaction conditions of Example 1, compound 47 was synthesized. The difference from Example 1 was that SM5 was replaced with M1, SM4 was replaced with M5-2, and SM2 was replaced with... Replace SM3 with The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1551.87, while the measured value was 1552.83.

[0078] Example 14: Synthesis of Compound 53 Following the synthesis steps and reaction conditions of Example 1, compound 53 was synthesized, the difference being that SM3 was replaced with... SM5 was replaced with M8 and SM1 was replaced with M3. The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1451.82, while the measured value was 1452.64.

[0079] Example 15: Synthesis of Compound 54 Following the synthesis steps and reaction conditions of Example 1, compound 54 was synthesized, the difference being that SM3 was replaced with... SM5 was replaced with M7 and SM1 was replaced with M3. The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1454.84, while the measured value was 1455.68.

[0080] Example 16: Synthesis of Compound 65 Following the synthesis steps and reaction conditions of Example 6, compound 65 was synthesized, the difference being that SM3 was replaced with... The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1401.71, while the measured value was 1402.37.

[0081] Example 17: Synthesis of Compound 80 Referring to the synthesis steps and method of Example 6, compound 80 was synthesized, the difference from Example 6 being that SM3 was replaced with The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1457.78, while the measured value was 1458.44.

[0082] Example 18: Synthesis of Compound 95 Referring to the synthesis steps and method of Example 6, compound 95 was synthesized, the difference from Example 6 being that SM3 was replaced with The product was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1511.82, while the measured value was 1512.56.

[0083] The following are several examples of applications of the compounds described in this invention in OLED devices to further illustrate the beneficial effects of the compounds. The materials used in the examples were either commercially available or synthesized in-house.

[0084] Manufacturing of OLED devices: As a reference fabrication method for one embodiment of the device, the present invention involves depositing a 50-500 nm ITO / Ag / ITO (ITO:Ag:ITO weight ratio = 1:(10-20):1) layer on an alkali-free glass substrate as the anode. Then, a hole injection layer (5 nm-20 nm), a hole transport layer (50-150 nm), a light-emitting auxiliary layer (5-120 nm), a light-emitting layer (20-50 nm), a hole blocking layer (5-20 nm), an electron transport layer (20-80 nm), and an electron injection layer (1-10 nm) are deposited on the anode. Following this, Mg and Ag (weight ratio 1:9, 10-15 nm) are co-deposited to form a semi-transparent cathode, and then a capping compound (30 nm-90 nm) is deposited. Finally, the light-emitting device is encapsulated using epoxy resin adhesive under a nitrogen atmosphere.

[0085] In a preferred embodiment, the OLED device provided by the present invention has the following structure: first, an alkali-free glass substrate is washed with isopropanol for 15 minutes using an ultrasonic cleaner, and then subjected to UV ozone washing treatment in the air for 30 minutes. The prepared substrate was deposited using vacuum evaporation. An ITO / Ag / ITO layer (ITO:Ag:ITO weight ratio = 1:10:1, 120nm) was deposited as the anode. Then, a hole injection layer (HT:PD, 10nm, 2%), a hole transport layer (HT, 130nm), a light-emitting auxiliary layer (BP1, 5nm), a blue light-emitting layer (body material: dopant material = BH:compound 1 (weight ratio 98:2, 30nm)), a hole blocking layer (HB, 5nm), an electron transport layer (ET:Liq = 1:1, 30nm), and an electron injection layer (Yb, 1nm) were sequentially deposited. Finally, Mg and Ag (weight ratio 1:9, 13nm) were co-deposited to form a semi-transparent cathode. A CPL layer (65nm) was then deposited as a capping layer. Finally, the light-emitting device was encapsulated using epoxy resin adhesive under a nitrogen atmosphere. This is referred to as Application Example 1. The molecular structural formulas of the relevant materials are shown below (particularly preferably selected from the following structures, but this does not mean that the invention is limited to the following structures): .

[0086] Application Examples 2-21 and Comparative Examples 1-3 were prepared using the method provided in Application Example 1 above, with the only difference being that the compounds listed in Table 1 were used as luminescent auxiliary materials to replace BP1 in Application Example 1 or to replace luminescent dopant compound 1 used in the luminescent layer of Application Example 1. The structures of Ref-BP and Ref-BD used in Comparative Examples 1-3 are as follows: .

[0087] Performance evaluation of OLED devices: The current of the OLED device at different voltages was measured using a Keithley 2365A digital nanovoltmeter, and then the current density of the OLED device at different voltages was obtained by dividing the current by the emitting area. The brightness and radiant energy flux density of the OLED device at different voltages were measured using a Konicaminolta CS-2000 spectroradiometer. Based on the current density and brightness of the OLED device at different voltages, the current density (10 mA / cm²) at the same voltage was obtained. 2 The operating voltage (Volt) and current efficiency (cd / A) are given by BI = E / CIEy, which refers to the Blue Index in blue light and is also a parameter measuring the luminous efficiency of blue light. E refers to the current efficiency, and CIEy refers to the ordinate color point obtained by substituting the wavelength of the device's emission half-peak into the CIE1930 software. The test data are shown in Table 1.

[0088] Table 1. Examples of Applications and Electroluminescence Properties of Composite Materials

[0089] As shown in Table 1, compared with Comparative Examples 1-3, Application Examples 1 to 21 exhibit higher blue light BI luminous efficiency. The performance improvement in each application example is based on the present invention's preferred combination of a luminescent dopant material obtained by combining triphenylsilane with alkyl-substituted carbazole fragments with a specific luminescent auxiliary material using naphthyl and dibenzofuran fragments. This combination better improves luminous efficiency, reduces device power consumption, and extends device lifespan.

[0090] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention.

Claims

1. An organic electroluminescent device, characterized in that, include Substrate layer; A first electrode is located on the substrate; An organic light-emitting functional layer is disposed on the first electrode; The second electrode is located on the organic light-emitting functional layer; The organic light-emitting functional layer includes a light-emitting layer, which comprises a doped material of formula I: ； In Formula I, X1 is selected from O or S; R1 and R2 each independently represent monosubstituted, disubstituted, or polysubstituted substances; R1, R2, R3, and R4 each independently represent hydrogen, deuterium, C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C5-C36 heteroaryl; the substituted or unsubstituted substances are selected from one or more of hydrogen, deuterium, C1-C12 alkyl, and C3-C24 cycloalkyl; "D" represents deuterium, and n is an integer from 0 to 15; The organic light-emitting functional layer further includes a light-emitting auxiliary layer, wherein the light-emitting auxiliary layer is a material with a structure of Formula II: ； Wherein, L, L1, and L2 are each independently selected from single bonds and C6-C30 arylene groups, and X is selected from O or S atoms; Ar1 ​​and Ar2 are each independently selected from deuterated or undeuterated C6-C30 aryl groups and deuterated or undeuterated C5-C36 heteroaryl groups; Ra and Rb are each independently selected from hydrogen, deuterium, and phenyl, and at least one of Ra and Rb is selected from phenyl; n1 is selected from integers from 0 to 3, and n2 is selected from integers from 0 to 4.

2. The organic electroluminescent device according to claim 1, characterized in that, In Formula I, R1 and R2 are each independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, C1-C4 alkyl-substituted or unsubstituted carbazole groups each time they appear; and at least one of them is selected from C1-C4 alkyl-substituted or unsubstituted carbazole groups.

3. The organic electroluminescent device according to claim 1, characterized in that, In Formula I, R1 is disubstituted or polysubstituted, and each time R1 appears, it is independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, C1-C4 alkyl-substituted or unsubstituted carbazolyl, and one of them is C1-C4 alkyl-substituted or unsubstituted carbazolyl; R2 is monosubstituted, disubstituted or polysubstituted, and each time R2 appears, it is selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, or the same or different from each other.

4. The organic electroluminescent device according to claim 1, characterized in that, In Formula I, R3 is independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, phenyl, tert-butylphenyl, and tetramethyltetrahydronaphthyl.

5. The organic electroluminescent device according to claim 1, characterized in that, In Formula I, R4 is independently selected from hydrogen, deuterium, methyl, ethyl, propyl, and tert-butyl.

6. The organic electroluminescent device according to claim 1, characterized in that, The doping material in the light-emitting layer is selected from any one or more of the following structures, where tBu represents tert-butyl and D represents deuterium: 。 7. The organic electroluminescent device according to claim 1, characterized in that, In Formula II, L1 and L2 are each independently selected from single bonds, phenylene, and naphthylene; Ar1 ​​and Ar2 are selected from the following groups, either deuterated or undeuterated: phenyl, naphthyl, phenyl-substituted naphthyl, and dibenzofuranyl.

8. The organic electroluminescent device according to claim 1, characterized in that, In Formula II, L is selected from phenylene or biphenylene.

9. The organic electroluminescent device according to claim 1, characterized in that, The light-emitting auxiliary layer is selected from any one or more of the following structures, where D represents deuterium: 。 10. The use of the organic electroluminescent device according to any one of claims 1-7 in the preparation of display or lighting devices.

11. A display or lighting device, characterized in that, The device comprises an organic electroluminescent device as described in any one of claims 1-7.

12. A composition, characterized in that, The composition comprises compounds of formula I: ； In Formula I, X1 is selected from O or S; R1 and R2 each independently represent monosubstituted, disubstituted, or polysubstituted substances; R1, R2, R3, and R4 each independently represent hydrogen, deuterium, C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C5-C36 heteroaryl; the substituted or unsubstituted substances are selected from one or more of hydrogen, deuterium, C1-C12 alkyl, and C3-C24 cycloalkyl; "D" represents deuterium, and n is an integer from 0 to 15; And materials including those with a Formula II structure: ； Wherein, L, L1, and L2 are each independently selected from single bonds and C6-C30 arylene groups, and X is selected from O or S atoms; Ar1 ​​and Ar2 are each independently selected from deuterated or undeuterated C6-C30 aryl groups and deuterated or undeuterated C5-C36 heteroaryl groups; Ra and Rb are each independently selected from hydrogen, deuterium, and phenyl, and at least one of Ra and Rb is selected from phenyl; n1 is selected from integers from 0 to 3, and n2 is selected from integers from 0 to 4.

Images