Heterocyclic compound composition and organic electroluminescent device

Abstract

The invention discloses a heterocyclic compound composition and an organic electroluminescent device. Wherein the heterocyclic compound combination comprises a hole injection layer compound and a light-emitting layer compound, the hole injection layer compound is selected from a first compound shown in the formula 1, the light-emitting layer compound contains a bi-component host material and a doping material, the bi-component host material comprises a first host and a second host, and the doping material comprises a second host and a third host. The first main body is selected from a compound shown in a formula 2, the second main body is selected from a compound shown in a formula 3-1 or a formula 3-2, the hole injection material (PD doped material) is matched with the GH bi-component main body material, and meanwhile, the first doped SP is used, so that the prepared device has excellent luminous efficiency and long service life. And meanwhile, by matching with the second doped GD, the luminous efficiency of the device and the device are further improved through the prepared sensitized device. # imgabs0 #, # imgabs1 #, # imgabs2 # and # imgabs3 #.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and in particular to a heterocyclic compound combination and an organic electroluminescence device. Background Art

[0002] An organic electroluminescent device has a structure including an anode and a cathode and an organic material layer therebetween. The organic layer is usually formed by a multilayer structure composed of different materials. Currently common organic layer structures include: a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer.

[0003] Research on improving the performance of organic electroluminescent devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and increasing the service life of the device. In order to continuously improve the performance of organic electroluminescent devices, it is necessary not only to continuously research and innovate organic electrophotoelectric functional materials to create higher performance organic electrofunctional materials, but also to study and design the structure and device matching of organic electroluminescent devices to produce organic electroluminescent devices with higher performance.

[0004] The patent with publication number "CN109912619A" discloses a compound that can be used in the hole injection layer On this basis, the following materials were further developed under the publication number of "CN115490704B" for application in the hole injection layer of organic electroluminescent devices: The patent CN109912619A adopts As a dual-component host material; the patent "CN115490704B" discloses that the luminescent layer can contain the following green light host materials The patent "CN119020024A" discloses As a hole injection layer, , As a device combination of two components, in order to optimize the device performance, further research and exploration is carried out on the basis of this study. It is necessary to develop and combine different organic electroluminescent materials to develop organic electroluminescent devices with excellent luminous efficiency and lifespan. Summary of the invention

[0005] The purpose of the present invention is to provide a heterocyclic compound combination based on the prior art.

[0006] Another object of the present invention is to provide an organic electroluminescent device containing the above heterocyclic compound combination.

[0007] The scheme of the present invention is as follows: A heterocyclic compound combination, comprising a hole injection layer compound and a light-emitting layer compound, wherein the hole injection layer compound is selected from a compound 1 shown in Formula 1: , where A1-A 10 Each is independently selected from: hydrogen, deuterium, fluorine, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl, and the substituent is selected from: hydrogen, deuterium, fluorine, fluorinated alkane, fluorinated alkoxy; The light-emitting layer compound contains a dual-component host material and a doping material, wherein the dual-component host material includes a first host and a second host, and the first host is selected from the compound shown in Formula 2: , wherein R1-R5 are each independently selected from deuterium, deuterated or undeuterated phenyl, R1-R5 contain at most one deuterated or undeuterated phenyl, R6-R 11 are each independently selected from hydrogen or deuterium, R 12 -R 19 are each independently selected from hydrogen, deuterium, deuterated or undeuterated phenyl, R 12 -R 19 contains at most one deuterated or undeuterated phenyl group, R 20 -R 24 Each independently selected from deuterated, deuterated or undeuterated phenyl, R 20 -R 24 Contains at most one deuterated or undeuterated phenyl group; The second host is selected from the compound represented by Formula 3-1 or Formula 3-2: , wherein Ar1, Ar2, Ar3, and Ar4 are each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 heteroaryl, and the substituent is hydrogen, deuterium, deuterated or undeuterated C1-C4 alkyl, deuterated or undeuterated C1-C5 cycloalkyl.

[0008] As a preferred embodiment of the present invention, Ar1, Ar2, Ar3, and Ar4 are each independently selected from phenyl, biphenyl, phenyl-substituted biphenyl, N-phenylcarbazolyl, dibenzofuran, phenyl-substituted dibenzofuran, triphenylene, phenanthryl, terphenyl, fluoranthene, and triphenyl[1,12-bcd]furanyl.

[0009] As a preferred solution of the present invention, the doping material adopts a single first doping or is composed of a first doping and a second doping, wherein the first doping is selected from the compound four shown in Formula 401 to Formula 405: Wherein: Y1-Y8 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and combinations thereof; Y9-Y 16 Each is independently hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and combinations thereof; Y 17 -Y 20 Each is independently hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, cyano, and combinations thereof; Y 20 , Y 21 Each independently derived from hydrogen or deuterium; Y 22 -Y 25 Each is independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C20 aryl, Y 22 -Y 25 Two adjacent ones of them can be joined or fused to form a phenyl group or a naphthyl group; In the substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, the alkyl, cycloalkyl, aryl and heteroaryl may be unsubstituted or may be substituted by one or more selected from deuterium, halogen, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino and combinations thereof; The second doping is a B / N type MR-TADF material.

[0010] As a preferred embodiment of the present invention, the second doping is selected from compounds represented by Formula 501 to Formula 516: , Among them Z1-Z 11 Each is independently selected from H, D, F, substituted or unsubstituted C1-C20 alkyl; Z 12 -Z 14 Each independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, Z 12- Z 14 Two adjacent ones are connected to form a ring or not; W1, W2, and W3 each independently represent a nitrogen atom or a boron atom, and only one of W1, W2, and W3 represents a nitrogen atom; α, β, θ, ε, and δ each independently represent 0 or 1, and α+β+θ+ε+δ≥1; M1, M2, M3, M4, and M5 independently represent a single bond, a sulfur atom, an oxygen atom, N(Z 15 )、B(Z 16 )、C(Z 17 ) (Z 18 ) or Si(Z 19 )(Z 20 );where Z 17 With Z 18 , Z 19 With Z 20 are connected to each other to form a ring or not; at least one of M1, M2, M3, M4, and M5 is not represented as a single bond; K1 to K 21 Each independently represents a nitrogen atom or CR, and R represents a hydrogen atom, protium, deuterium, tritium, a cyano group, a halogen atom, a C1-C20 alkyl group, a C1-C20 alkyl substituted silyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a C6-C20 aryl group, or an amine group substituted with a C5-C30 heteroaryl group; M6 represents a sulfur atom or an oxygen atom; Z 21 -Z 23 Each is independently selected from H, D, F, a sulfur atom, an oxygen atom, a C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, Z 21 -Z 23 Two adjacent Z are connected to each other to form a ring or not; 24 -Z 37 Each is independently selected from H, D, F, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl; Z 38-Z 43 Each is independently selected from H, D, F, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl; Z 44 -Z 47 Each is independently selected from H, D, F, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl; the dotted lines in Formula 508-Formula 510 represent being connected by a single bond or not, and only two of the three dotted lines in each general formula represent being connected by a single bond; Z 48 -Z 55 Each is independently selected from H, D, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted heteroaryl containing one or more heteroatoms; the dotted line in Formula 512 indicates connection by a single bond or no connection, and only two of the three dotted lines in each general formula indicate connection by a single bond; Z 56 -Z 65 Each is independently selected from H, D, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, and substituted or unsubstituted C3-C30 heteroaryl.

[0011] As a preferred embodiment of the present invention, the hole injection layer compound is selected from the following compounds of the structural formula: .

[0012] As a preferred embodiment of the present invention, the first host is selected from the following compounds: .

[0013] As a preferred embodiment of the present invention, the second host is selected from the following compounds: .

[0014] As a preferred embodiment of the present invention, the first doping agent is selected from the following compounds: .

[0015] As a preferred embodiment of the present invention, the second doping agent is selected from the following compounds: .

[0016] As a preferred embodiment of the present invention, the hole transport layer compound is selected from the compound represented by Formula 601 or Formula 602: , wherein X1, X2, X3, X4, and X5 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6-C20 aryl, and the substituent is hydrogen or deuterium.

[0017] As a preferred embodiment of the present invention, X1 and X2 are hydrogen or tert-butyl, and X3, X4 and X5 are each independently selected from hydrogen, deuterium, methyl and deuterated methyl.

[0018] As a preferred embodiment of the present invention, the hole transport layer compound is selected from the following compounds: 。

[0019] An organic electroluminescent device comprises a first electrode, a second electrode and an organic layer formed between the first electrode and the second electrode, wherein the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer; wherein the hole injection layer is selected from the compound represented by formula 1 of the present invention, and the light-emitting layer contains the dual-component main material of the present invention and a doping material.

[0020] Preferably, the hole transport layer contains the compound represented by Formula 601 or Formula 602 of the present invention.

[0021] Beneficial effects of the present invention: The compounds of the present invention all have suitable molecular weight, low sublimation temperature and evaporation temperature, good thermal stability, and can effectively improve the device preparation yield. The N-type compound of the present invention can form a good Premix material with the P-type compound of the present invention, and has good P / N stability and mass production stability during the evaporation process, and the formed Premix material has a more balanced carrier mobility, thereby greatly improving the efficiency and life of the device. The device prepared by using the hole injection material (PD doping material) of the present invention, with the GH two-component main material of the present invention, and using the first doping SP of the present invention at the same time, has excellent luminous efficiency and life. At the same time, with the second doping GD, the sensitized device prepared further improves the luminous efficiency and device of the device. Using the main material of the present invention, only a small amount of SP (3%-5% weight percentage of the main material) is used with 0.3%-0.8% of the B / N type GD material in the present invention, and better efficiency and longer life are achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 A schematic diagram of the structure of an organic electroluminescent device provided by the present invention; The numbers in the figure represent: 1-anode, 2-hole injection layer, 3-hole transport layer, 4-electron blocking layer, 5-light-emitting layer, 6-hole blocking layer, 7-electron transport layer, 8-electron injection layer, 9-cathode. DETAILED DESCRIPTION

[0023] The following further illustrates and describes embodiments of various aspects. It should be understood that the description herein is not intended to limit the claims to the specific aspects described. On the contrary, it is intended to cover substitutions, modifications and equivalents that may be included in the spirit and scope of the present disclosure defined by the appended claims.

[0024] As used herein, in "substituted" or "unsubstituted", the term "substituted" means that at least one hydrogen in the group is re-coordinated with deuterium, a hydrocarbon group, a hydrocarbon derivative group, a halogen, or a cyano group (-CN). The term "unsubstituted" means that at least one hydrogen in the group is not re-coordinated with deuterium, a hydrocarbon group, a hydrocarbon derivative group, a halogen, or a cyano group (-CN). Examples of hydrocarbon groups or hydrocarbon derivative groups may include C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C5 to C30 heteroaryl, C1 to C30 alkylamino, C6 to C30 arylamino, C6 to C30 heteroarylamino, C6 to C30 arylheteroarylamino, etc., but are not limited thereto.

[0025] Deuterium in the present invention refers to a stable isotope of hydrogen, also known as heavy hydrogen, and its element symbol is D.

[0026] The aromatic group in the present invention refers to an all-carbon monocyclic or condensed polycyclic group of 6 to 30 carbon atoms, having a completely conjugated π electron system. Non-limiting examples of aromatic groups include phenyl, naphthyl, anthracenyl, biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, triphenyl[1,12-bcd]furanyl, phenanthrenyl, and the like.

[0027] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0028] Synthesis example 1:

[0029]

[0030] Process: PM8013 (15 g, 42 mmol, 1 eq), PM8015 (17.5 g, 46.6 mmol, 1.1 eq), potassium carbonate (12.8 g, 92.6 mol, 2.2 eq), Pd(PPd3)4 (0.9 g, 0.78 mmol, 0.02 eq) and toluene / ethanol / water (250 ml + 65 ml + 65 ml) were added into a 1 L three-necked flask. The temperature was raised and refluxed for 5-18 h under N2 protection. The reaction was monitored by HPLC. PM8013 ≤ 0.5%.

[0031] Post-treatment: After the reaction is completed, stop the reaction, stir and cool, filter, rinse the filter cake with water and ethanol respectively, heat the filter cake with 1L toluene to dissolve it, pass it through silica gel and activated carbon while hot, evaporate about 200ml of toluene from the filtrate, cool and stir to crystallize to room temperature, filter, recrystallize the filter cake twice with toluene (600ml*2), filter, and dry the filter cake at 85℃ to obtain 12.89g of off-white solid with HPLC purity of 99.9867% and yield of 53.8%.

[0032] Synthesis example 2:

[0033]

[0034] Process: PM8015 (48.4 g, 0.1 mol, 1 eq), PM8016 (23.5 g, 0.101 mol, 1.01 eq), sodium tert-butoxide (19.2 g, 0.2 mol, 2 eq), tri-tert-butylphosphine (8.08 ml, 0.004 mol, 0.04 eq) and toluene (730 ml) were added into a 2 L reaction bottle. Tridibenzylideneacetone palladium (1.83 g, 0.002 mol, 0.02 eq) was added under N2 protection. After the addition was completed, the temperature was raised to 90-110 °C and stirred for reaction. PM8015 was monitored by HPLC to be ≤1%.

[0035] Post-treatment: stop heating, add 4.4L ethanol, stir and crystallize overnight, filter, and dry the filter cake at 85°C to obtain 60.69g of gray solid. The above crude product was heated to reflux with toluene (3V / M) to dissolve, add ethanol (6V / M), heat and reflux for 10min, then cool and stir to crystallize overnight, filter, heat the filter cake with DCM (about 10V / M) to dissolve, evaporate most of the DCM to 200ml, cool to room temperature and stir for 30min, filter, heat the filter cake with DCM (about 40V / M) to dissolve again, evaporate most of the DCM to 200ml, cool to room temperature and stir for 30min, filter, repeat the refining three times, and dry the filter cake at 85°C to obtain 53.53g of off-white solid, HPLC purity 99.9903%, yield 84%.

[0036] Synthesis example 3:

[0037]

[0038] Process: PM8015 (48.4 g, 0.1 mol, 1 eq), PM8020 (16.5 g, 0.105 mol, 1.05 eq), sodium tert-butoxide (19.2 g, 0.2 mol, 0.2 eq), tri-tert-butylphosphine (8.08 ml, 0.004 mol, 0.04 eq) and toluene (730 ml) were added into a 2 L reaction bottle. Tridibenzylideneacetone palladium (1.83 g, 0.002 mol, 0.02 eq) was added under N2 protection. After the addition was completed, the temperature was raised to 90-110 °C and stirred for reaction. PM8015 was monitored by HPLC to be ≤0.5%.

[0039] Post-treatment: After the reaction is qualified, stop heating, add 730ml of water and stir to separate the liquids, extract the aqueous phase with toluene (365ml*2), combine the organic phases, filter through silica gel, and concentrate the filtrate under reduced pressure to obtain 69.69g of brown oil. After the above oil is heated to reflux with toluene to dissolve, add ethanol, stir and crystallize overnight, filter, heat the filter cake with toluene to reflux to dissolve, add ethanol, stir and crystallize for 2~3h, filter, heat the filter cake with toluene to reflux again to dissolve, pass silica gel and activated carbon while hot, stir and crystallize overnight, filter, and air dry the filter cake at 85℃ to obtain 38.53g of off-white solid, HPLC purity 99.9649%, yield 68.7%.

[0040] Synthesis example 4:

[0041]

[0042] Process: CP1050-SM2 (58g, 0.13mol, 1eq), CP1050-SM1 (52.39g, 0.132mol, 1.02eq), potassium carbonate (54g, 0.39mol, 3eq), toluene / ethanol / water (1L+0.5L+0.3L) were added to a 5L three-necked flask. Tetrakistriphenylphosphine palladium (3g, 2.6mmol, 0.02eq) was added under N2 protection. After the addition was completed, the temperature was raised and refluxed to react until CP1050-SM2 ≤1%.

[0043] Post-treatment: stop heating, add 1.9L ethanol and 0.3L water, stir and crystallize overnight, filter, rinse the filter cake with water, rinse with 5L ethanol, dry the filter cake at 85°C, heat the crude product with toluene to dissolve it, filter it through silica gel while hot, evaporate 1 / 2 of the toluene from the filtrate, cool and stir to crystallize, filter, recrystallize the filter cake with toluene 5 times, filter, and obtain 45g of off-white solid with HPLC purity of 99.9933% and yield of 54.4%.

[0044] Device performance test: Application Example 1: ITO was used as the reflective layer anode substrate material, and its surface was treated with water, acetone, and N2 plasma in sequence; On the ITO anode substrate, 10 nm of the HT material HT-1 of the present invention (doped with 3% of the PD material PD-9 of the present invention) is deposited to form a hole injection layer (HIL); 100 nm of the HT material HT-1 of the present invention is evaporated on the hole injection layer (HIL) to form a hole transport layer (HTL); Vacuum evaporate GP-1 on the hole transport layer (HTL) to form a second hole transport layer (GPL) with a thickness of 10 nm; Compound P-1 prepared in Example 1 of the present invention and N-1 material of the present invention were co-evaporated at a ratio of 5:5 as luminescent host materials, and SP-1 of the present invention was evaporated as a doping material (the amount of SP-1 was 8% of the total weight of compound P-1 and N-1) on the second hole transport layer (GPL) to form a luminescent layer with a thickness of 20 nm; HB-1 was evaporated onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm; ET-1 and LiQ were co-evaporated onto the hole blocking layer (HBL) at a ratio of 5:5 to obtain an electron transport layer (ETL) with a thickness of 30 nm; Magnesium (Mg) and silver (Ag) were mixed in a ratio of 9:1 and evaporated onto the electron transport layer (ETL) to form an electron injection layer (EIL) with a thickness of 50 nm. After that, silver (Ag) is evaporated onto the electron injection layer to form a cathode with a thickness of 100nm, and DNTPD with a thickness of 50nm is deposited on the cathode sealing layer. In addition, the cathode surface is sealed with a UV curable adhesive and a seal cap containing a dehumidifier to protect the organic electroluminescent device from being affected by oxygen or moisture in the atmosphere, thereby preparing an organic electroluminescent device.

[0045]

[0046] Comparative Example 1.1 An organic electroluminescent device was prepared by replacing P-1 in Application Example 1 with D1-P in CN109912619A, replacing N-1 in Application Example 1 with D1-N in CN109912619A, and replacing SP-1 in Application Example 1 with D1-SP in CN109912619A to obtain Comparative Example 1.1; Comparative Example 1.2 D1-P in CN109912619A is used to replace P-1 in Application Example 1, and D1-N in CN109912619A is used to replace N-1 in Application Example 1, and an organic electroluminescent device is prepared accordingly to obtain Comparative Example 1.2; Comparative Example 2

[0047] D1-P in CN109912619A is used to replace P-1 in Application Example 1, and D2-N in CN115490704B is used to replace N-1 in Application Example 1, and an organic electroluminescent device is prepared accordingly to obtain Comparative Example 2; Comparative Example 3

[0048] D3-P in CN119020024A was used to replace P-1 in Application Example 1, and D3-N in CN119020024A was used to replace N-1 in Application Example 1, and an organic electroluminescent device was prepared accordingly to obtain Comparative Example 3; Comparative Example 4

[0049] HAT-CN in CN112028883A was used to replace PD-9 in Application Example 1, and P-6 was used to replace P-1 in Application Example 1, and an organic electroluminescent device was prepared accordingly to obtain Comparative Example 4;

[0050] Application Example 2-11: The compounds P-3, P-6, P-10, P-14, P-22, P-41, P-43, P-44, P-49 and P-63 of the present invention are used to replace P-1 in Application Example 1, and organic electroluminescent devices are prepared accordingly to obtain Application Examples 2-11.

[0051]

[0052] Application Example 12-27: The compounds N-2, N-3, N-6, N-7, N-11, N-20, N-29, N-38, N-74, N-75, N-110, N-120, N-126, N-130, N-140 and N-146 of the present invention are used to replace N-1 in Application Example 1, and organic electroluminescent devices are prepared accordingly to obtain Application Examples 12-27.

[0053]

[0054] Application Examples 28-31: The compounds PD-5, PD-7, PD-11 and PD-14 of the present invention were used to replace N-1 in Application Example 1, and organic electroluminescent devices were prepared accordingly to obtain Application Examples 28-31.

[0055]

[0056] Application Examples 32-35: The SP-1 in Application Example 1 was replaced by the compounds SP-2, SP-30, SP-56 and SP-57 of the present invention respectively, and organic electroluminescent devices were prepared accordingly to obtain Application Examples 32-35.

[0057]

[0058] Application Examples 36-38: The compounds HT-2, HT-7 and HT-47 of the present invention were used to replace HT-1 in Application Example 1, and organic electroluminescent devices were prepared accordingly to obtain Application Examples 36-38.

[0059]

[0060] The organic electroluminescent devices prepared in application examples 1-38 and control examples 1-3 were tested respectively. The voltage, luminous efficiency, life, and luminous life of the organic electroluminescent devices prepared in control examples 1-3 and application examples 1-38 were tested. The luminous life test obtained the luminous life T97% data (the time when the luminous brightness is reduced to 97% of the initial brightness). The test equipment was a TEO luminescent device life test system. The test results are shown in Table 1.

[0061] Experimental Group Hole injection layer Hole transport layer First Subject Second subject First doping Voltage (V) Luminous efficiency (Cd / A) life Emitting color Comparative Example 1.1 PD-9 HT-1 D1-N P-6 D1-SP 3.81 126.3 95 Green Light Comparative Example 1.2 PD-9 HT-1 D1-N P-6 SP-1 3.76 129.5 97 Green Light Comparative Example 2 PD-9 HT-1 D2-N P-6 SP-1 3.79 139.1 99 Green Light Comparative Example 3 PD-9 HT-1 N-2 D3-P SP-1 3.71 141.6 106 Green Light Comparative Example 4 HAT-CN HT-1 N-1 P-6 SP-1 3.73 132.6 100% Green Light Application Example 1 PD-9 HT-1 N-1 P-1 SP-1 3.40 209 144% Green Light Application Example 2 PD-9 HT-1 N-1 P-3 SP-1 3.42 206 145% Green Light Application Example 3 PD-9 HT-1 N-1 P-6 SP-1 3.49 215 141% Green Light Application Example 4 PD-9 HT-1 N-1 P-10 SP-1 3.43 204 146% Green Light Application Example 5 PD-9 HT-1 N-1 P-14 SP-1 3.45 218 148% Green Light Application Example 6 PD-9 HT-1 N-1 P-22 SP-1 3.44 217 147% Green Light Application Example 7 PD-9 HT-1 N-1 P-41 SP-1 3.53 183 126% Green Light Application Example 8 PD-9 HT-1 N-1 P-43 SP-1 3.55 195 137% Green Light Application Example 9 PD-9 HT-1 N-1 P-44 SP-1 3.56 183 129% Green Light Application Example 10 PD-9 HT-1 N-1 P-49 SP-1 3.58 199 122% Green Light Application Example 11 PD-9 HT-1 N-1 P-63 SP-1 3.52 185 120% Green Light Application Example 12 PD-9 HT-1 N-2 P-1 SP-1 3.46 214 145% Green Light Application Example 13 PD-9 HT-1 N-3 P-1 SP-1 3.41 210 147% Green Light Application Example 14 PD-9 HT-1 N-6 P-1 SP-1 3.44 209 143% Green Light Application Example 15 PD-9 HT-1 N-7 P-1 SP-1 3.49 202 148% Green Light Application Example 16 PD-9 HT-1 N-11 P-1 SP-1 3.41 205 141% Green Light Application Example 17 PD-9 HT-1 N-20 P-1 SP-1 3.45 204 149% Green Light Application Example 18 PD-9 HT-1 N-29 P-1 SP-1 3.45 207 145% Green Light Application Example 19 PD-9 HT-1 N-38 P-1 SP-1 3.43 207 144% Green Light Application Example 20 PD-9 HT-1 N-74 P-1 SP-1 3.57 199 137% Green Light Application Example 21 PD-9 HT-1 N-75 P-1 SP-1 3.55 183 133% Green Light Application Example 22 PD-9 HT-1 N-110 P-1 SP-1 3.52 196 124% Green Light Application Example 23 PD-9 HT-1 N-120 P-1 SP-1 3.59 194 135% Green Light Application Example 24 PD-9 HT-1 N-126 P-1 SP-1 3.57 197 133% Green Light Application Example 25 PD-9 HT-1 N-130 P-1 SP-1 3.59 191 120% Green Light Application Example 26 PD-9 HT-1 N-140 P-1 SP-1 3.57 182 126% Green Light Application Example 27 PD-9 HT-1 N-146 P-1 SP-1 3.56 195 128% Green Light Application Example 28 PD-5 HT-1 N-1 P-1 SP-1 3.40 209 143% Green Light Application Example 29 PD-7 HT-1 N-1 P-1 SP-1 3.48 203 147% Green Light Application Example 30 PD-11 HT-1 N-1 P-1 SP-1 3.46 216 149% Green Light Application Example 31 PD-14 HT-1 N-1 P-1 SP-1 3.44 219 142% Green Light Application Example 32 PD-9 HT-1 N-1 P-1 SP-2 3.40 212 141% Green Light Application Example 33 PD-9 HT-1 N-1 P-1 SP-30 3.43 203 145% Green Light Application Example 34 PD-9 HT-1 N-1 P-1 SP-56 3.47 204 144% Green Light Application Example 35 PD-9 HT-1 N-1 P-1 SP-57 3.46 218 148% Green Light Application Example 36 PD-9 HT-2 N-1 P-1 SP-1 3.45 219 149% Green Light Application Example 37 PD-9 HT-7 N-1 P-1 SP-1 3.41 217 143% Green Light Application Example 38 PD-9 HT-47 N-1 P-1 SP-1 3.44 215 140% Green Light As shown in Table 1 above, the composition of the present invention is composed of a first host and a second host to form a luminescent host material, and compound 1 is used as a hole injection material, which realizes a high-performance, high-stability and low-power OLED device, and provides new possibilities for the development of display and lighting technology. Using benzodioxazole compounds as hole injection materials; triazine mother core and connecting carbazole (deuterated or undeuterated), deuterated phenyl substituted dibenzofuran, phenyl (deuterated or undeuterated) on the side chain as the first host; undeuterated dicarbazole or indole carbazole as the second host, this structural design can effectively improve the hole injection efficiency.

[0062] Biscarbazole compounds have high hole mobility and can effectively promote the transport of holes. The triazine core has good electron transport ability and can effectively promote the transport of electrons. This structural design makes the recombination efficiency of holes and electrons in the light-emitting layer higher, thereby improving the luminous efficiency of the device. The introduction of deuterated groups can significantly improve the thermal and chemical stability of the molecule.

[0063] Comparison with the patent "CN109912619A": The patent "CN109912619A" uses a dicarbazole compound as the main body one, and the triazine mother core is connected to indolecarbazole, phenyl, and phenyl on the side chain as the main body two. In the improved structure, a deuterated phenyl-substituted dibenzofuran is connected to the side chain, which further improves the hole injection efficiency. The deuterated phenyl-substituted dibenzofuran structure significantly improves the thermal stability, while the structure in the patent "CN109912619A" has relatively poor thermal stability. The improved structure further improves the luminous efficiency by optimizing the energy level structure.

[0064] Comparison with the patent "CN115490704B": The patent "CN115490704B" discloses that the green light host material can be a triazine core and connected to carbazole, phenyl-substituted dibenzofuran, and deuterated phenyl on the side chain. In the improved structure, deuterated phenyl-substituted dibenzofuran is connected to the side chain, which further improves the hole injection efficiency. The deuterated phenyl-substituted dibenzofuran structure significantly improves the thermal stability, and although the structure in the patent "CN115490704B" also has a deuterated group, the substituent of dibenzofuran is not deuterated. The improved structure further improves the luminous efficiency by optimizing the energy level structure.

[0065] Comparison with the patent "CN119020024A": The patent "CN119020024A" uses a deuterated dicarbazole compound as the main body one, a triazine mother core and connects carbazole, deuterated phenyl-substituted dibenzofuran, and phenyl on the side chain as the main body two.

[0066] The present invention adopts a biscarbazole compound as the main body one, and a triazine mother core and a carbazole, a deuterated phenyl-substituted dibenzofuran, and a phenyl group are connected on the side chain as the main body two. The biscarbazole compound has a high hole mobility and can more effectively promote the transmission of holes, thereby improving the hole injection efficiency. Although the deuterium substitution on the biscarbazole is removed from the second main body of the present invention, the deuterated phenyl-substituted dibenzofuran structure is still retained, and still has a high thermal stability. By matching the hole injection material of the present invention, the device performance is improved, the device cost is effectively reduced, and the device performance is optimized.

[0067] Comparison with the patent "CN112028883B": The patent "CN112028883B" uses a dicarbazole compound as the main body one, a triazine mother core and connects carbazole, deuterated phenyl-substituted dibenzofuran, and phenyl on the side chain as the main body two.

[0068] The present invention adopts a dicarbazole compound as the main body one, a triazine mother core and connects carbazole, deuterated phenyl-substituted dibenzofuran and phenyl on the side chain as the main body two, and on this basis, the hole injection material used in the present invention is used to further improve the device performance, effectively optimizing the device performance.

[0069] Application Example 39: ITO was used as the reflective layer anode substrate material, and its surface was treated with water, acetone, and N2 plasma in sequence; On top of the ITO anode substrate, 10 nm of HT-1 doped with 3% PD-9 was deposited to form a hole injection layer (HIL); On top of the hole injection layer (HIL), 100 nm of HT-1 was evaporated to form a hole transport layer (HTL); Vacuum evaporate GP-1 on the hole transport layer (HTL) to form a second hole transport layer (GPL) with a thickness of 10 nm; After the GPL evaporation is completed, the light-emitting layer (EML) of the OLED light-emitting device is prepared, using the compound P-1 of the present invention and the compound N-1 of the present invention as the main material, SP-49 as the first doping material, and the compound GD-1 as the second doping material, the mass ratio of P-1, N-1, SP-49 and compound GD-1 is 66.5:30:3:0.5, and the thickness of the light-emitting layer is 30 nm; HB-1 was evaporated onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm; ET-1 and LiQ were co-evaporated onto the hole blocking layer (HBL) at a ratio of 5:5 to obtain an electron transport layer (ETL) with a thickness of 30 nm; Magnesium (Mg) and silver (Ag) were mixed in a ratio of 9:1 and evaporated onto the electron transport layer (ETL) to form an electron injection layer (EIL) with a thickness of 50 nm. Thereafter, silver (Ag) is evaporated onto the electron injection layer to form a cathode with a thickness of 100 nm, and a DNTPD with a thickness of 50 nm is deposited on the cathode sealing layer. In addition, the cathode surface is sealed with a UV curable adhesive and a sealing film (seal cap) containing a dehumidifier to protect the organic electroluminescent device from being affected by oxygen or moisture in the atmosphere. Thus, an organic electroluminescent device is prepared.

[0070]

[0071] Comparative Example 5 D5-N in CN116178403A replaces N-1 in Application Example 1, HI-1 replaces PD-9 in Application Example 1, and other parts are consistent with Application Example 1, thereby manufacturing an organic electroluminescent device.

[0072] Comparative Example 6 D6-N in the embodiment of CN118206574A is used to replace N-1 in application example 1; HI-1 is used to replace PD-9 in application example 1, and GD-13 is used to replace GD-1 in application example 1. The other parts are consistent with application example 1, and an organic electroluminescent device is manufactured accordingly.

[0073] Comparative Example 7 D7-N in the embodiment of CN111377957A is used to replace N-1 in application example 1; HI-1 is used to replace PD-9 in application example 1, and GD-27 is used to replace GD-1 in application example 1. The other parts are consistent with application example 1, and an organic electroluminescent device is manufactured accordingly.

[0074] Comparative Example 8 D8-N in the embodiment of CN116925114A was used to replace N-1 in Application Example 1; HI-1 was used to replace PD-9 in Application Example 1; GD-49 was used to replace GD-1 in Application Example 1, and an organic electroluminescent device was manufactured accordingly.

[0075] Comparative Example 9 D9-P in the embodiment of CN116396311A is used to replace P-1 in application example 1, D9-N is used to replace N-1 in application example 1; HI-1 is used to replace PD-9 in application example 1, and GD-59 is used to replace GD-1 in application example 1, and an organic electroluminescent device is manufactured accordingly.

[0076] Comparative Example 10 D10-N in the embodiment of CN116655664A was used to replace N-1 in application example 1; HI-1 was used to replace PD-9 in application example 1; GD-71 was used to replace GD-1 in application example 1, and an organic electroluminescent device was manufactured accordingly.

[0077] Comparative Example 11 D11-N in the embodiment of CN118852220 is used to replace N-1 in application example 1; HI-1 is used to replace PD-9 in application example 1, and GD-75 is used to replace GD-1 in application example 1, and an organic electroluminescent device is manufactured accordingly;

[0078] Application Examples 40-49 The compounds GD-13, GD-27, GD-49, GD-59, GD-71, GD-75, GD-78, GD-79, GD-84 and GD-86 of the present invention are used to replace GD-1 in Application Example 1, and organic electroluminescent devices are prepared therefrom to obtain Application Examples 40-49; Application Example 50 The SP-49 in Application Example 1 is replaced by the compound SP-1 of the present invention, and an organic electroluminescent device is prepared therefrom to obtain Application Example 50; Application Examples 51-54

[0079] The compounds PD-5, PD-7, PD-11 and PD-14 of the present invention are used to replace PD-9 in Application Example 1, and organic electroluminescent devices are prepared therefrom to obtain Application Examples 51-54; The organic electroluminescent devices prepared in application examples 39-54 and control examples 5-11 were tested respectively. The voltage, luminous efficiency, life, and luminous life of the organic electroluminescent devices prepared in control examples 5-11 and application examples 39-54 were tested. The luminous life test obtained the luminous life T97% data (the time when the luminous brightness is reduced to 97% of the initial brightness). The test equipment was a TEO luminescent device life test system. The test results are shown in Table 2.

[0080] Table 2 Experimental Group Hole injection layer First Subject Second subject First doping Second doping Voltage (V) Luminous efficiency (Cd / A) life Emitting color Comparative Example 5 HI-1 D5-N P-1 SP-49 GD-1 3.70 158 103% Green Light Comparative Example 6 HI-1 D6-N P-1 SP-49 GD-13 3.84 166 109% Green Light Comparative Example 7 HI-1 D7-N P-1 SP-49 GD-27 3.89 142 102% Green Light Comparative Example 8 HI-1 D8-N P-1 SP-49 GD-49 3.78 163 91% Green Light Comparative Example 9 HI-1 D9-N D9-P SP-49 GD-59 3.75 154 97% Green Light Comparative Example 10 HI-1 D10-N P-1 SP-49 GD-71 3.87 169 93% Green Light Comparative Example 11 HI-1 D11-N P-1 SP-49 GD-75 3.83 145 91% Green Light Application Example 39 PD-9 N-1 P-1 SP-49 GD-1 3.25 237 157% Green Light Application Example 40 PD-9 N-1 P-1 SP-49 GD-13 3.28 239 148 Green Light Application Example 41 PD-9 N-1 P-1 SP-49 GD-27 3.31 228 155% Green Light Application Example 42 PD-9 N-1 P-1 SP-49 GD-49 3.29 234 159% Green Light Application Example 43 PD-9 N-1 P-1 SP-49 GD-59 3.34 225 166% Green Light Application Example 44 PD-9 N-1 P-1 SP-49 GD-71 3.29 233 145% Green Light Application Example 45 PD-9 N-1 P-1 SP-49 GD-75 3.25 231 169% Green Light Application Example 46 PD-9 N-1 P-1 SP-49 GD-78 3.26 246 157% Green Light Application Example 47 PD-9 N-1 P-1 SP-49 GD-79 3.27 244 155% Green Light Application Example 48 PD-9 N-1 P-1 SP-49 GD-84 3.22 258 165% Green Light Application Example 49 PD-9 N-1 P-1 SP-49 GD-86 3.21 251 164% Green Light Application Example 50 PD-9 N-1 P-1 SP-1 GD-1 3.27 235 144% Green Light Application Example 51 PD-5 N-1 P-1 SP-49 GD-1 3.21 239 154% Green Light Application Example 52 PD-7 N-1 P-1 SP-49 GD-1 3.24 246 163% Green Light Application Example 53 PD-11 N-1 P-1 SP-49 GD-1 3.27 234 166% Green Light Application Example 54 PD-14 N-1 P-1 SP-49 GD-1 3.25 236 157% Green Light It can be seen from Table 2 above that compared with the two-component main material of TADF and the first doping material in Comparative Examples 5-11, Examples 39-54 of the present invention use TADF and the first doping material with a compound of a main structure of dicarbazole or indolecarbazole as the P-type main body, a triazine main structure and a dibenzofuran compound substituted with deuterated phenyl on its side chain as the N-type main body, which is applied to organic electroluminescent devices to achieve high performance, high stability and long life OLED devices; and compared with Application Examples 1-38, Application Examples 39-54 use a combination of the first doping and the second doping, which achieves better efficiency and longer life on the basis of the combination of the light-emitting main body and the hole injection layer of the present invention, providing new possibilities for the development of display and lighting technologies.

Claims

1. A heterocyclic compound combination, characterized in that: It includes a hole injection layer compound and a light-emitting layer compound, wherein the hole injection layer compound is selected from a compound 1 shown in Formula 1: , where A1-A 10 Each is independently selected from: hydrogen, deuterium, fluorine, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl, and the substituent is selected from: hydrogen, deuterium, fluorine, fluorinated alkane, fluorinated alkoxy; The light-emitting layer compound contains a dual-component host material and a doping material, wherein the dual-component host material includes a first host and a second host, and the first host is selected from the compound shown in Formula 2: , wherein R1-R5 are each independently selected from deuterium, deuterated or undeuterated phenyl, R1-R5 contain at most one deuterated or undeuterated phenyl, R6-R 11 are each independently selected from hydrogen or deuterium, R 12 -R 19 are each independently selected from hydrogen, deuterium, deuterated or undeuterated phenyl, R 12 -R 19 contains at most one deuterated or undeuterated phenyl group, R 20 -R 24 Each independently selected from deuterated, deuterated or undeuterated phenyl, R 20 -R 24 Contains at most one deuterated or undeuterated phenyl group; The second host is selected from the compound represented by Formula 3-1 or Formula 3-2: , wherein Ar1, Ar2, Ar3, and Ar4 are each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 heteroaryl, and the substituent is hydrogen, deuterium, deuterated or undeuterated C1-C4 alkyl, deuterated or undeuterated C1-C5 cycloalkyl.

2. The heterocyclic compound combination according to claim 1, characterized in that: The doping material adopts a single first doping or is composed of a first doping and a second doping at the same time, wherein the first doping is selected from the compound 4 shown in Formula 401 to Formula 405: Wherein: Y1-Y8 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and combinations thereof; Y9-Y 16 Each is independently hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and combinations thereof; Y 17 -Y 20 Each is independently hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, cyano, and combinations thereof; Y 20 , Y 21 Each independently derived from hydrogen or deuterium; Y 22 -Y 25 Each is independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C20 aryl, Y 22 -Y 25 Two adjacent ones of them can be joined or fused to form a phenyl group or a naphthyl group; In the substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, the alkyl, cycloalkyl, aryl and heteroaryl may be unsubstituted or may be substituted by one or more selected from deuterium, halogen, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino and combinations thereof; The second doping is a B / N type MR-TADF material.

3. The heterocyclic compound combination according to claim 2, characterized in that: The second doping agent is selected from compounds represented by Formula 501 to Formula 516: , where Z1-Z 11 Each is independently selected from H, D, F, substituted or unsubstituted C1-C20 alkyl; Z 12 -Z 14 Each independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, Z 12- Z 14 Two adjacent ones are connected to form a ring or not; W1, W2, and W3 each independently represent a nitrogen atom or a boron atom, and only one of W1, W2, and W3 represents a nitrogen atom; α, β, θ, ε, and δ each independently represent 0 or 1, and α+β+θ+ε+δ≥1; M1, M2, M3, M4, and M5 independently represent a single bond, a sulfur atom, an oxygen atom, N(Z 15 )、B(Z 16 )、C(Z 17 ) (Z 18 ) or Si(Z 19 )(Z 20 );where Z 17 With Z 18 , Z 19 With Z 20 are connected to each other to form a ring or not; at least one of M1, M2, M3, M4, and M5 is not represented as a single bond; K1 to K 21 Each independently represents a nitrogen atom or CR, and R represents a hydrogen atom, protium, deuterium, tritium, a cyano group, a halogen atom, a C1-C20 alkyl group, a C1-C20 alkyl substituted silyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a C6-C20 aryl group, or an amine group substituted with a C5-C30 heteroaryl group; M6 represents a sulfur atom or an oxygen atom; Z 21 -Z 23 Each is independently selected from H, D, F, a sulfur atom, an oxygen atom, a C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, Z 21 -Z 23 Two adjacent Z are connected to each other to form a ring or not; 24 -Z 37 Each is independently selected from H, D, F, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl; Z 38 -Z 43 Each is independently selected from H, D, F, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl; Z 44 -Z 47 Each is independently selected from H, D, F, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl; the dotted lines in Formula 508-Formula 510 represent being connected by a single bond or not, and only two of the three dotted lines in each general formula represent being connected by a single bond; Z 48 -Z 55 Each is independently selected from H, D, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted heteroaryl containing one or more heteroatoms; the dotted line in Formula 512 indicates connection by a single bond or no connection, and only two of the three dotted lines in each general formula indicate connection by a single bond; Z 56 -Z 65 Each is independently selected from H, D, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, and substituted or unsubstituted C3-C30 heteroaryl.

4. The heterocyclic compound combination as claimed in claim 1, characterized in that: The hole injection layer compound is selected from the following compounds: 。 5. The heterocyclic compound combination according to claim 1, characterized in that: The first host is selected from the following compounds: 。 6. The heterocyclic compound combination according to claim 2, characterized in that: The second host is selected from the following compounds: 。 7. The heterocyclic compound combination according to claim 2, characterized in that: The first doping compound is selected from the following structural formula: 。 8. The heterocyclic compound combination according to claim 1, characterized in that: The second doping compound is selected from the following structural formula: 。 9. The heterocyclic compound combination according to claim 1, characterized in that: It includes a hole transport layer compound, wherein the hole transport layer compound is selected from the compound represented by Formula 601 or Formula 602: , wherein X1, X2, X3, X4, and X5 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6-C20 aryl, and the substituent is hydrogen or deuterium.

10. The heterocyclic compound combination according to claim 9, characterized in that: The hole transport layer compound is selected from the following compounds: 。 11. An organic electroluminescent device, characterized in that It includes a first electrode, a second electrode and an organic layer formed between the first electrode and the second electrode, wherein the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer; wherein the hole injection layer is selected from the compound represented by formula 1 according to claim 1, and the light-emitting layer contains the dual-component main material and the doping material according to claim 1.

12. The organic electroluminescent device according to claim 11, characterized in that The hole transport layer contains the compound represented by Formula 601 or Formula 602 according to claim 9.

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