Heterocyclic compound combination and organic electroluminescent device

Abstract

Disclosed in the present disclosure are a heterocyclic compound combination and an organic electroluminescent device. 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 compound I represented by formula 1, the light-emitting layer compound contains a two-component host material and a dopant material, the two-component host material comprises a first host and a second host, the first host is selected from a compound represented by formula (2), and the second host is selected from a compound represented by formula (3-1) or formula (3-2). By using a hole injection material (a PD-doped material) of the present disclosure, in combination with a GH two-component host material of the present disclosure, and using a first dopant SP of the present disclosure, a prepared device has excellent luminous efficiency and service life. Furthermore, by additionally using a second dopant GD, the luminous efficiency of a prepared sensitized device is further improved, and the device is further optimized.

Description

A combination of heterocyclic compounds and an organic electroluminescent device

[0001] Cross-references to related applications

[0002] This disclosure claims priority to Chinese Patent Application No. 202510184089X, filed on February 19, 2025, entitled "A Heterocyclic Compound Combination and an Organic Electroluminescent Device", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the field of organic electroluminescence technology, and more specifically, to a combination of heterocyclic compounds and an organic electroluminescent device. Background Technology

[0004] Organic electroluminescent devices have a structure that includes an anode and a cathode and an organic material layer between them. The organic layer is usually formed by a multilayer structure composed of different materials. Common organic layer structures include: hole injection layer, hole transport layer, electron blocking layer, light emission layer, hole blocking layer, electron transport layer, and electron injection layer.

[0005] Research on improving the performance of organic electroluminescent devices includes reducing the driving voltage, increasing luminous efficiency, and extending lifespan. To continuously improve the performance of organic electroluminescent devices, it is necessary not only to continuously research and innovate organic electroluminescent functional materials to create higher-performance materials, but also to study and design the structure and device configuration of organic electroluminescent devices to produce devices with even higher performance.

[0006] The patent with publication number CN109912619A discloses a compound that can be applied to a hole injection layer. Based on this, the following material, disclosed in publication number CN115490704B, was further developed for application in the hole injection layer of organic electroluminescent devices. The patent CN109912619A adopts As a two-component host material, patent CN115490704B discloses that the luminescent layer can include the following green light host material. The patent disclosed in CN119020024A is As a hole injection layer As a device combination with two main components, further research and exploration are needed to optimize device performance. This requires the development and combination of different organic electroluminescent materials to develop organic electroluminescent devices with excellent luminous efficiency and lifetime. Summary of the Invention

[0007] The purpose of this disclosure is to provide a combination of heterocyclic compounds based on the prior art.

[0008] Another object of this disclosure is to provide an organic electroluminescent device containing the above-described combination of heterocyclic compounds.

[0009] The disclosed solution is as follows:

[0010] A heterocyclic compound assembly comprising a hole injection layer compound and a light-emitting layer compound, wherein the hole injection layer compound is selected from compound one of Formula 1:

[0011] Where A1-A 10 Each of the following 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, wherein the substituent is selected from: hydrogen, deuterium, fluorine, fluoroalkane, fluoroalkoxy.

[0012] The luminescent layer compound contains a two-component host material and a dopant material, wherein the two-component host material includes a first host and a second host, and the first host is selected from the compound shown in Formula 2:

[0013] R1-R5 are each independently selected from deuterated, deuterated, or undeuterated phenyl groups, and R1-R5 contain at most one deuterated or undeuterated phenyl group. 11 Each is independently selected from hydrogen or deuterium, R 12 -R 19 Each phenyl group is independently selected from hydrogen, deuterium, deuterated, or undeuterated phenyl groups, R 12 -R 19 It contains at most one deuterated or undeuterated phenyl group, R 20 -R 24 Each phenyl group is independently selected from deuterated, deuterated, or undeuterated phenyl groups, R 20 -R 24 It contains at most one deuterated or undeuterated phenyl group;

[0014] The second subject is selected from the compounds shown in Formula 3-1 or Formula 3-2:

[0015] Ar1, Ar2, Ar3, and Ar4 are each independently selected from substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C5-C30 heteroaryl groups, wherein the substituents are hydrogen, deuterium, deuterated or undeuterated C1-C4 alkyl groups, or deuterated or undeuterated C1-C5 cycloalkyl groups.

[0016] As a preferred embodiment of this disclosure, Ar1, Ar2, Ar3, and Ar4 are each independently selected from phenyl, biphenyl, phenyl-substituted biphenyl, N-phenylcarbazolyl, dibenzofuran, phenyl-substituted dibenzofuran, triphenylene, phenanthrene, terphenyl, fluoranthene, and triphenyl[1,12-bcd]furanyl.

[0017] As a preferred embodiment of this disclosure, the doped material is a single first dopant or consists of both a first dopant and a second dopant, wherein the first dopant is selected from compounds four shown in formulas 401-405: Among them: 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.

[0018] Y9-Y 16 Each of the following is independent of 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;

[0019] Y 17 -Y 20 Each of the following is independent of 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.

[0020] Y 20 Y 21 Each is independently derived from hydrogen or deuterium;

[0021] Y 22 -Y 25 Each aryl group, independently derived from hydrogen, deuterium, or substituted or unsubstituted C6-C20, Y 22 -Y 25 Two adjacent molecules can combine or fuse to form a phenyl or naphthalene group;

[0022] The alkyl, cycloalkyl, aryl, and heteroaryl groups are selected from 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 groups, wherein the alkyl, cycloalkyl, aryl, and heteroaryl groups may be unsubstituted or may be substituted by one or more of the following: 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, thioalkyl, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0023] The second doping is a B / N type MR-TADF material.

[0024] As a preferred embodiment of this disclosure, the second dopant is selected from compounds represented by formulas 501-516:

[0025] Among them, Z1-Z 11 Each is independently selected from H, D, F, substituted or unsubstituted C1-C20 alkyl groups; Z 12 -Z 14 Each is independently selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C6-C20 aryl groups, Z 12- Z 14 Two adjacent connections in the middle may form a loop or not;

[0026] W1, W2, and W3 each independently represent either nitrogen or boron atoms, 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, and N(Z) atom. 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 Interconnected 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 21Each is independently represented as a nitrogen atom or CR, where R represents one of the following: hydrogen atom, protium, deuterium, tritium, cyano, halogen atom, C1-C20 alkyl, C1-C20 alkyl-substituted silyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl, C6-C20 aryl, or C5-C30 heteroaryl-substituted amino group; M6 represents a sulfur atom or an oxygen atom; Z 21 -Z 23 Each element is independently selected from H, D, F, sulfur atom, oxygen atom, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl, Z. 21 -Z 23 Two adjacent elements in the middle may be connected to form a loop or not; Z 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;

[0027] 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;

[0028] 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; in Formulas 508-510, the dashed lines indicate whether they are connected by a single bond or not, and in each general formula, only two of the three dashed lines indicate that they are connected by a single bond.

[0029] 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 dashed lines in Formula 512 indicate whether they are connected by a single bond or not, and only two of the three dashed lines in each general formula indicate that they are connected by a single bond.

[0030] Z 56 -Z 65 Each is independently selected from H, D, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl.

[0031] As a preferred embodiment of this disclosure, the hole injection layer compound is selected from compounds with the following structural formulas:

[0032] As a preferred embodiment of this disclosure, the first component is selected from compounds with the following structural formulas:

[0033] As a preferred embodiment of this disclosure, the second component is selected from compounds with the following structural formulas:

[0034] As a preferred embodiment of this disclosure, the first dopant is selected from compounds with the following structural formulas:

[0035] As a preferred embodiment of this disclosure, the second dopant is selected from compounds with the following structural formulas:

[0036] As a preferred embodiment of this disclosure, it includes a hole transport layer compound selected from compounds of formula 601 or formula 602:

[0037] X1, X2, X3, X4, and X5 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C5 alkyl, or substituted or unsubstituted C6-C20 aryl, wherein the substituent is hydrogen or deuterium.

[0038] As a preferred embodiment of this disclosure, X1 and X2 are hydrogen or tert-butyl, and X3, X4, and X5 are each independently selected from hydrogen, deuterium, methyl, or deuterated methyl.

[0039] As a preferred embodiment of this disclosure, the hole transport layer compound is selected from compounds with the following structural formulas:

[0040] An organic electroluminescent device includes a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode. 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. The hole injection layer is selected from compounds represented by Formula 1 of this disclosure, and the light-emitting layer contains a two-component host material and a dopant material of this disclosure.

[0041] Preferably, the hole transport layer contains a compound represented by Formula 601 or Formula 602 of this disclosure.

[0042] The beneficial effects of this disclosure are:

[0043] The compounds disclosed herein all possess suitable molecular weights, low sublimation and evaporation temperatures, and good thermal stability, effectively improving device fabrication yield. The N-type compounds of this disclosure can form excellent premix materials with the P-type compounds of this disclosure, exhibiting good P / N stability and mass production stability during evaporation. Furthermore, the formed premix materials possess more balanced carrier mobility, thereby significantly improving device efficiency and lifetime. Devices fabricated using the hole injection material (PD-doped material) of this disclosure, combined with the GH dual-component host material of this disclosure, and simultaneously using the first doped SP of this disclosure, exhibit excellent luminous efficiency and lifetime. The sensitized devices fabricated by combining the second doped GD further improve luminous efficiency and lifetime. Using the host material of this disclosure, only a small amount of SP (3%-5% by weight of host material) combined with 0.3%-0.8% of the B / N type GD material of this disclosure is needed to achieve better efficiency and longer lifetime. Attached Figure Description

[0044] Figure 1 is a schematic diagram of the structure of the organic electroluminescent device provided in this disclosure;

[0045] The numbers in the diagram 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, and 9-cathode. Detailed Implementation

[0046] Embodiments of various aspects are further illustrated and described below. It should be understood that the description herein is not intended to limit the claims to the specific aspects described. Rather, it is intended to cover substitutions, modifications, and equivalents that may be included within the spirit and scope of this disclosure as defined by the appended claims.

[0047] As used herein, in the context of “substituted” or “unsubstituted”, the term “substituted” means that at least one hydrogen in the group is recoordinated with a deuterium, alkyl group, hydrocarbon derivative group, halogen, or cyano (-CN). The term “unsubstituted” means that at least one hydrogen in the group is not recoordinated with a deuterium, alkyl group, hydrocarbon derivative group, halogen, or cyano (-CN). Examples of alkyl or hydrocarbon derivative groups may include, but are not limited to, 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 aromaticamino, C6 to C30 heteroarylamino, C6 to C30 aryl heteroarylamino, etc.

[0048] In this disclosure, deuterium refers to a stable isotope of hydrogen, also known as heavy hydrogen, with the element symbol D.

[0049] In this disclosure, an aromatic group refers to a monocyclic or fused polycyclic group with 6 to 30 carbon atoms, possessing a fully conjugated π-electron system. Non-limiting examples of aryl groups include phenyl, naphthyl, anthraceneyl, biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, benzo[1,12-bcd]furanyl, phenanthrene, etc.

[0050] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0051] Synthesis example 1:

[0052] Procedure: PM8013 (15g, 42mmol, 1eq), PM8015 (17.5g, 46.6mmol, 1.1eq), potassium carbonate (12.8g, 92.6mol, 2.2eq), Pd(PPd3)4 (0.9g, 0.78mmol, 0.02eq), and toluene / ethanol / water (250ml + 65ml + 65ml) were added to a 1L three-necked flask. Under N2 protection, the mixture was refluxed for 5–18 h. The concentration of PM8013 was monitored by HPLC and kept ≤0.5%.

[0053] Post-processing: After the reaction was complete, the reaction was stopped, the mixture was stirred and cooled, and then filtered. The filter cake was washed with water and ethanol, respectively. The filter cake was then dissolved in 1L of toluene by heating. While still hot, the mixture was passed through silica gel and activated carbon. About 200ml of toluene was distilled off from the filtrate. The mixture was cooled and stirred to crystallize to room temperature, and then filtered. The filter cake was recrystallized twice with toluene (600ml*2), filtered again, and dried at 85℃ by forced air to obtain 12.89g of off-white solid with an HPLC purity of 99.9867% and a yield of 53.8%.

[0054] Synthesis example 2:

[0055] Procedure: 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 to a 2 L reaction flask. Under N2 protection, tris(dibenzylacetone)palladium (1.83 g, 0.002 mol, 0.02 eq) was added. After the addition was complete, the temperature was raised to 90–110 °C and the reaction was stirred. HPLC monitoring showed that PM8015 was ≤1%.

[0056] Post-processing: Heating was stopped, 4.4 L of ethanol was added and stirred to induce crystallization overnight. The mixture was then filtered, and the filter cake was dried at 85 °C to obtain 60.69 g of gray solid. The crude product was dissolved in toluene (3 V / M) under reflux, followed by the addition of ethanol (6 V / M). The mixture was then heated under reflux for 10 min, cooled, stirred, and allowed to crystallize overnight. The mixture was filtered, and the filter cake was dissolved in DCM (approximately 10 V / M) under reflux. Most of the DCM was evaporated to 200 ml, and the mixture was cooled to room temperature and stirred for 30 min. The mixture was then filtered, and the filter cake was again dissolved in DCM (approximately 40 V / M) under reflux. Most of the DCM was evaporated to 200 ml, and the mixture was cooled to room temperature and stirred for 30 min. The mixture was then filtered, and the purification process was repeated three times. The filter cake was dried at 85 °C to obtain 53.53 g of off-white solid with an HPLC purity of 99.9903% and a yield of 84%.

[0057] Synthesis example 3:

[0058] Procedure: 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 to a 2 L reaction flask. Under N2 protection, tris(2-benzylacetone)palladium (1.83 g, 0.002 mol, 0.02 eq) was added. After the addition was complete, the temperature was raised to 90–110 °C and the reaction was stirred. The PM8015 concentration was monitored by HPLC to be ≤0.5%.

[0059] Post-processing: After the reaction was successful, heating was stopped, 730 ml of water was added, and the mixture was stirred and separated. The aqueous phase was extracted with toluene (365 ml * 2). The organic phases were combined and filtered through silica gel. The filtrate was concentrated under reduced pressure to obtain 69.69 g of a brown oily substance. The oily substance was dissolved by refluxing with toluene, ethanol was added, and the mixture was stirred to crystallize overnight. The mixture was filtered, and the filter cake was dissolved by refluxing with toluene. Ethanol was added, and the mixture was stirred to crystallize for 2-3 hours. The mixture was filtered, and the filter cake was dissolved by refluxing with toluene again. While still hot, the mixture was filtered through silica gel and activated carbon. The filtrate was stirred to crystallize overnight. The mixture was filtered, and the filter cake was dried at 85°C with a forced-air drying process to obtain 38.53 g of an off-white solid with an HPLC purity of 99.9649% and a yield of 68.7%.

[0060] Synthesis example 4:

[0061] Procedure: Add CP1050-SM2 (58g, 0.13mol, 1eq) and CP1050-SM1 (52.39g) to a 5L three-necked flask.

[0062] 0.132 mol (1.02 eq), potassium carbonate (54 g, 0.39 mol, 3 eq), toluene / ethanol / water (1 L + 0.5 L + 0.3 L), under N2 protection, add tetrakis(triphenylphosphine)palladium (3 g, 2.6 mmol, 0.02 eq), after which the mixture is heated to reflux until CP1050-SM2≤1%.

[0063] Post-processing: Stop heating, add 1.9 L ethanol and 0.3 L water, stir and crystallize overnight, filter, rinse the filter cake with water and 5 L ethanol, dry the filter cake at 85 °C, dissolve the crude product in toluene by heating, filter it through silica gel while hot, distill off half of the toluene from the filtrate, cool and stir to crystallize, filter, recrystallize the filter cake with toluene 5 times, filter again to obtain 45 g of off-white solid with HPLC purity of 99.9933% and yield of 54.4%.

[0064] Device performance testing:

[0065] Application Example 1:

[0066] ITO was used as the anode substrate material for the reflective layer, and its surface was treated sequentially with water, acetone, and N2 ions.

[0067] A hole injection layer (HIL) is formed by depositing 10 nm of the disclosed HT material HT-1 (doped with 3% of the disclosed PD material PD-9) on top of the ITO anode substrate.

[0068] A hole transport layer (HTL) is formed by depositing 100 nm of the disclosed HT material HT-1 above the hole injection layer (HIL);

[0069] GP 1 was vacuum-deposited above the hole transport layer (HTL) to form a second hole transport layer (GPL) with a thickness of 10 nm.

[0070] The compound P-1 prepared in Example 1 of this disclosure and the N-1 material of this disclosure are co-deposited as light-emitting host materials in a 5:5 ratio. SP-1 of this disclosure is used as a dopant material (the amount of SP-1 is 8% of the total weight of compound P-1 and N-1) and evaporated on the second hole transport layer (GPL) to form a light-emitting layer with a thickness of 20 nm.

[0071] HB-1 was deposited onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm;

[0072] ET-1 and LiQ were co-deposited onto the hole blocking layer (HBL) in a 5:5 ratio to obtain an electron transport layer (ETL) with a thickness of 30 nm.

[0073] Magnesium (Mg) and silver (Ag) are mixed in a 9:1 ratio and vapor-deposited onto the electron transport layer (ETL) to form an electron injection layer (EIL) with a thickness of 50 nm.

[0074] Subsequently, silver (Ag) was deposited onto the electron injection layer to form a 100 nm thick cathode. A 50 nm thick DNTPD was then deposited on the cathode sealing layer.

[0075] In addition, the cathode surface is sealed with a UV-curable adhesive and a sealing cap containing a desiccant to protect the organic electroluminescent device from the influence of atmospheric oxygen or moisture. This process yields the organic electroluminescent device.

[0076] Comparative Example 1.1

[0077] Comparative Example 1.1 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.

[0078] Comparative Example 1.2

[0079] Comparative Example 1.2 was prepared by replacing P-1 in Application Example 1 with D1-P in CN109912619A and replacing N-1 in Application Example 1 with D1-N in CN109912619A.

[0080] Comparative Example 2

[0081] Comparative Example 2 was prepared by replacing P-1 in Application Example 1 with D1-P in CN109912619A and replacing N-1 in Application Example 1 with D2-N in CN115490704B.

[0082] Comparative Example 3

[0083] Comparative Example 3 was prepared by replacing P-1 in Application Example 1 with D3-P in CN119020024A and replacing N-1 in Application Example 1 with D3-N in CN119020024A.

[0084] Comparative Example 4

[0085] Comparative Example 4 was prepared by replacing PD-9 in Application Example 1 with HAT-CN in CN112028883A and replacing P-1 in Application Example 1 with P-6.

[0086] Application Example 2-11:

[0087] Application Examples 2-11 were obtained by replacing P-1 in Application Example 1 with compounds P-3, P-6, P-10, P-14, P-22, P-41, P-43, P-44, P-49, and P-63 respectively, which are matched according to the present disclosure.

[0088] Application Example 12-27:

[0089] In Application Example 1, N-1 was replaced by 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, respectively, and organic electroluminescent devices were prepared accordingly to obtain Application Examples 12-27.

[0090] Application Example 28-31:

[0091] Application Examples 28-31 were obtained by replacing N-1 in Application Example 1 with compounds PD-5, PD-7, PD-11, and PD-14 respectively, which are matched according to the present disclosure, and preparing organic electroluminescent devices accordingly.

[0092] Application Examples 32-35:

[0093] Application Examples 32-35 were obtained by replacing SP-1 in Application Example 1 with compounds SP-2, SP-30, SP-56, and SP-57 respectively, which are matched according to the present disclosure, and organic electroluminescent devices were prepared accordingly.

[0094] Application Examples 36-38:

[0095] Application Examples 36-38 were obtained by replacing HT-1 in Application Example 1 with compounds HT-2, HT-7, and HT-47 respectively, which are matched according to the present disclosure, and preparing organic electroluminescent devices accordingly.

[0096] Organic electroluminescent devices (OLEDs) prepared in Application Examples 1-38 and Control Examples 1-3 were tested respectively. Voltage, luminous efficiency, lifetime, and luminous lifetime were measured for both. The luminous lifetime test yielded the luminous lifetime T97% data (the time it takes for the luminous brightness to decrease to 97% of its initial brightness). The testing equipment was a TEO OLED lifetime testing system. The test results are shown in Table 1.

[0097] Table 1

[0098] As shown in Table 1 above, the composition disclosed herein comprises a first host and a second host as the light-emitting host material, and compound one as the hole injection material, achieving a high-performance, high-stability, and low-power OLED device, providing new possibilities for the development of display and lighting technologies. The first host uses a benzodioxazole compound as the hole injection material; a triazine core with carbazole (deuterated or undeuterated), deuterated phenyl-substituted dibenzofuran, or phenyl (deuterated or undeuterated) linked to its side chain; and an undeuterated biscarbazole or indolocarbazole as the second host. This structural design effectively improves hole injection efficiency.

[0099] Bicarbazole compounds exhibit high hole mobility, effectively promoting hole transport. The triazine core possesses excellent electron transport capabilities, further enhancing electron transport. This structural design results in higher recombination efficiency of holes and electrons in the luminescent layer, thereby improving the device's luminous efficiency. The introduction of deuterated groups significantly improves the molecule's thermal and chemical stability.

[0100] Comparison with patent CN109912619A:

[0101] The patent CN109912619A uses a biscarbazole compound as the first host, with a triazine core and indolecarbazole, phenyl, and phenyl linked to the side chains as the second host. In the improved structure, deuterated phenyl-substituted dibenzofuran is linked to the side chains, which further improves hole injection efficiency. The deuterated phenyl-substituted dibenzofuran structure significantly improves thermal stability, while the structure in the CN109912619A patent has relatively poor thermal stability. The improved structure further improves luminescence efficiency by optimizing the energy level structure.

[0102] Comparison with patent CN115490704B:

[0103] Patent CN115490704B discloses that the main material for green light can be a triazine core with carbazole, phenyl-substituted dibenzofuran, or deuterated phenyl groups attached to the side chains. In the improved structure, deuterated phenyl-substituted dibenzofuran is attached to the side chains, further enhancing hole injection efficiency. The deuterated phenyl-substituted dibenzofuran structure significantly improves thermal stability, while the structure in patent CN115490704B, although also containing deuterated groups, does not deuterate the substituents on the dibenzofuran. The improved structure, through optimized energy level structure, further enhances luminescence efficiency.

[0104] Comparison with patent CN119020024A:

[0105] The patent CN119020024A uses a deuterated biscarbazole compound as the main body, and a triazine core with carbazole, deuterated phenyl-substituted dibenzofuran, and phenyl linked to the side chain as the second main body.

[0106] This disclosure employs a biscarbazole compound as the primary host, and a triazine core with carbazole, a deuterated phenyl-substituted dibenzofuran, and a phenyl group attached to its side chains as the secondary host. The biscarbazole compound exhibits high hole mobility, effectively promoting hole transport and thus improving hole injection efficiency. While the deuteration substitution on the biscarbazole is removed from the secondary host, the deuterated phenyl-substituted dibenzofuran structure is retained, maintaining high thermal stability. Combined with the hole injection material of this disclosure, device performance is enhanced, effectively reducing device cost and optimizing device performance.

[0107] Comparison with patent CN112028883B:

[0108] The patent CN112028883B uses a biscarbazole compound as the main body, and a triazine core with carbazole, deuterated phenyl-substituted dibenzofuran, and phenyl linked to the side chain as the second main body.

[0109] This disclosure uses a biscarbazole compound as the first host, and a triazine core with carbazole, deuterated phenyl-substituted dibenzofuran, and phenyl linked to the side chain as the second host. Based on this, the hole injection material used in this disclosure is combined to further improve the device performance and effectively optimize the device performance.

[0110] Application Example 39:

[0111] ITO was used as the anode substrate material for the reflective layer, and its surface was treated sequentially with water, acetone, and N2 ions.

[0112] A 10 nm layer of HT-1 doped with 3% PD-9 is deposited on top of the ITO anode substrate to form a hole injection layer (HIL); a 100 nm layer of HT-1 is then deposited on top of the hole injection layer (HIL) to form a hole transport layer (HTL).

[0113] GP-1 was vacuum-deposited above the hole transport layer (HTL) to form a second hole transport layer (GPL) with a thickness of 10 nm. After the GPL deposition, the emissive layer (EML) of the OLED light-emitting device was fabricated. Compounds P-1 and N-1 of this disclosure were used as host materials, SP-49 was used as the first dopant, and compound GD-1 was used as the second dopant. The mass ratio of P-1, N-1, SP-49 and compound GD-1 was 66.5:30:3:0.5, and the thickness of the emissive layer was 30 nm.

[0114] HB-1 was deposited onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm;

[0115] ET-1 and LiQ were co-deposited onto the hole blocking layer (HBL) in a 5:5 ratio to obtain an electron transport layer (ETL) with a thickness of 30 nm.

[0116] Magnesium (Mg) and silver (Ag) are mixed in a 9:1 ratio and vapor-deposited onto the electron transport layer (ETL) to form an electron injection layer (EIL) with a thickness of 50 nm.

[0117] Subsequently, silver (Ag) is vapor-deposited onto the electron injection layer to form a cathode with a thickness of 100 nm. A 50 nm thick DNTPD is then deposited on the cathode sealing layer. Furthermore, the cathode surface is sealed with a UV-curable adhesive and a sealing cap containing a desiccant to protect the organic electroluminescent device from the influence of atmospheric oxygen or moisture. Thus, an organic electroluminescent device is prepared.

[0118] Comparative Example 5

[0119] By replacing N-1 in Application Example 1 with D5-N from CN116178403A, and replacing PD-9 in Application Example 1 with HI-1, and keeping the rest the same as Application Example 1, an organic electroluminescent device was fabricated.

[0120] Comparative Example 6

[0121] In the CN118206574A embodiment, D6-N is used to replace N-1 in Application Example 1; HI-1 is used to replace PD-9 in Application Example 1; GD-13 is used to replace GD-1 in Application Example 1; and the other parts are the same as in Application Example 1. Based on this, an organic electroluminescent device is fabricated.

[0122] Comparative Example 7

[0123] In the CN111377957A embodiment, D7-N is used to replace N-1 in Application Example 1; HI-1 is used to replace PD-9 in Application Example 1; GD-27 is used to replace GD-1 in Application Example 1; and the rest is the same as in Application Example 1. Based on this, an organic electroluminescent device is fabricated.

[0124] Comparative Example 8

[0125] An organic electroluminescent device was fabricated by replacing N-1 in Application Example 1 with D8-N in the embodiment of CN116925114A; replacing PD-9 in Application Example 1 with HI-1; and replacing GD-1 in Application Example 1 with GD-49.

[0126] Comparative Example 9

[0127] An organic electroluminescent device was fabricated by replacing P-1 in Application Example 1 with D9-P in the embodiment of CN116396311A, replacing N-1 in Application Example 1 with D9-N, replacing PD-9 in Application Example 1 with HI-1, and replacing GD-1 in Application Example 1 with GD-59.

[0128] Comparative Example 10

[0129] An organic electroluminescent device was fabricated by replacing N-1 in Application Example 1 with D10-N in the CN116655664A embodiment; replacing PD-9 in Application Example 1 with HI-1; and replacing GD-1 in Application Example 1 with GD-71.

[0130] Comparative Example 11

[0131] An organic electroluminescent device was fabricated by replacing N-1 in Application Example 1 with D11-N in the embodiment of CN118852220; replacing PD-9 in Application Example 1 with HI-1; and replacing GD-1 in Application Example 1 with GD-75.

[0132] Application Examples 40-49

[0133] By replacing GD-1 in Application Example 1 with compounds GD-13, GD-27, GD-49, GD-59, GD-71, GD-75, GD-78, GD-79, GD-84, and GD-86 disclosed herein, organic electroluminescent devices were prepared to obtain Application Examples 40-49.

[0134] Application Example 50

[0135] Application Example 50 was obtained by replacing SP-49 in Application Example 1 with the compound SP-1 disclosed herein, and preparing an organic electroluminescent device accordingly.

[0136] Application Examples 51-54

[0137] Application Examples 51-54 were obtained by replacing PD-9 in Application Example 1 with compounds PD-5, PD-7, PD-11, and PD-14 as described in this disclosure, and organic electroluminescent devices were prepared accordingly.

[0138] The organic electroluminescent devices prepared in Application Examples 39-54 and Control Examples 5-11 were tested respectively. Voltage, luminous efficiency, lifetime, and luminous lifetime were measured for the organic electroluminescent devices prepared in Control Examples 5-11 and Application Examples 39-54. The luminous lifetime test yielded the luminous lifetime T97% data (the time it takes for the luminous brightness to decrease to 97% of the initial brightness). The testing equipment was a TEO light-emitting device lifetime testing system. The test results are shown in Table 2.

[0139] Table 2

[0140] As shown in Table 2 above, compared to the two-component host material of TADF and the first dopant in Comparative Examples 5-11, the compounds of TADF and the first dopant combined with the biscarbazole or indolocarbazole host structure used in Examples 39-54 of this disclosure serve as the P-type host, and the triazine host structure with deuterated phenyl-substituted dibenzofuran compounds on its side chains serve as the N-type host. When applied to organic electroluminescent devices, this results in high-performance, high-stability, and long-lifetime OLED devices. Furthermore, compared to Application Examples 1-38, Application Examples 39-54, using a combination of the first and second dopant, achieve better efficiency and longer lifespan based on the host material and hole injection layer combination of this disclosure, providing new possibilities for the development of display and lighting technologies. Industrial applicability

[0141] The compounds disclosed herein all possess suitable molecular weights, low sublimation and evaporation temperatures, and good thermal stability, effectively improving device fabrication yield. The N-type compounds of this disclosure can form excellent premix materials with the P-type compounds of this disclosure, exhibiting good P / N stability and mass production stability during evaporation. Furthermore, the formed premix materials possess more balanced carrier mobility, thereby significantly improving device efficiency and lifetime. Devices fabricated using the hole injection material (PD doped material) of this disclosure, combined with the GH dual-component host material of this disclosure, and simultaneously using the first doped SP of this disclosure, exhibit excellent luminous efficiency and lifetime. The sensitized devices fabricated by combining the second doped GD further improve the luminous efficiency and lifetime. Using the host material of this disclosure, only a small amount of SP (3%-5% by weight of host material) combined with 0.3%-0.8% of the B / N type GD material of this disclosure is needed to achieve better efficiency and longer lifetime.

Claims

1. A combination of heterocyclic compounds, 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 compound one shown in Formula 1: Where A1-A 10 Each of the following 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, wherein the substituent is selected from: hydrogen, deuterium, fluorine, fluoroalkane, fluoroalkoxy. The luminescent layer compound contains a two-component host material and a dopant material, wherein the two-component host material includes a first host and a second host, and the first host is selected from the compound shown in Formula 2: R1-R5 are each independently selected from deuterated, deuterated, or undeuterated phenyl groups, and each of R1-R5 contains at most one... A deuterated or undeuterated phenyl group, R6-R 11 Each is independently selected from hydrogen or deuterium, R 12 -R 19 Each phenyl group is independently selected from hydrogen, deuterium, deuterated, or undeuterated phenyl groups, R 12 -R 19 It contains at most one deuterated or undeuterated phenyl group, R 20 -R 24 Each phenyl group is independently selected from deuterated, deuterated, or undeuterated phenyl groups, R 20 -R 24 It contains at most one deuterated or undeuterated phenyl group; The second subject is selected from the compounds shown in Formula 3-1 or Formula 3-2: Ar1, Ar2, Ar3, and Ar4 are each independently selected from those that have been substituted or not. The substituents are C6-C30 aryl groups, substituted or unsubstituted C5-C30 heteroaryl groups, wherein the substituents are hydrogen, deuterium, deuterated or undeuterated C1-C4 alkyl groups, or deuterated or undeuterated C1-C5 cycloalkyl groups.

2. The heterocyclic compound combination as described in claim 1, characterized in that, The doped material is a single first dopant or consists of both a first dopant and a second dopant, wherein the first dopant is selected from compounds four shown in formulas 401-405: Among them: 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 of the following is independent of 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 of the following is independent of 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 is independently derived from hydrogen or deuterium; Y 22 -Y 25 Each aryl group, independently derived from hydrogen, deuterium, or substituted or unsubstituted C6-C20, Y 22 -Y 25 Two adjacent molecules can combine or fuse to form a phenyl or naphthalene group; The alkyl, cycloalkyl, aryl, and heteroaryl groups are selected from 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 groups, wherein the alkyl, cycloalkyl, aryl, and heteroaryl groups may be unsubstituted or may be substituted by one or more of the following: 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, thioalkyl, sulfinyl, sulfonyl, phosphin, and combinations thereof. The second doping is a B / N type MR-TADF material.

3. The heterocyclic compound combination as described in claim 2, characterized in that, The second dopant is selected from compounds represented by formulas 501-516: Among them, Z1-Z 11 Each is independently selected from H, D, F, substituted or unsubstituted C1-C20 alkyl groups; Z 12 -Z 14 Each is independently selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C6-C20 aryl groups, Z 12- Z 14 Two adjacent connections in the middle may form a loop or not; W1, W2, and W3 each independently represent either nitrogen or boron atoms, 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, and N(Z) atom. 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 Interconnected 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 is independently represented as a nitrogen atom or CR, where R represents one of the following: hydrogen atom, protium, deuterium, tritium, cyano, halogen atom, C1-C20 alkyl, C1-C20 alkyl-substituted silyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl, C6-C20 aryl, or C5-C30 heteroaryl-substituted amino group; M6 represents a sulfur atom or an oxygen atom; Z 21 -Z 23 Each element is independently selected from H, D, F, sulfur atom, oxygen atom, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl, Z. 21 -Z 23 Two adjacent elements in the middle may be connected to form a loop or not; Z 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; in Formulas 508-510, the dashed lines indicate whether they are connected by a single bond or not, and in each general formula, only two of the three dashed lines indicate that they are 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 dashed lines in Formula 512 indicate whether they are connected by a single bond or not, and only two of the three dashed lines in each general formula indicate that they are connected by a single bond. Z 56 -Z 65 Each is independently selected from H, D, C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl.

4. The heterocyclic compound combination as described in claim 1, characterized in that, The hole injection layer compound is selected from compounds with the following structural formulas:

5. The heterocyclic compound combination as described in claim 1, characterized in that, The first host is selected from compounds with the following structural formulas:

6. The heterocyclic compound combination as described in claim 2, characterized in that, The second host is selected from compounds with the following structural formulas:

7. The heterocyclic compound combination as described in claim 2, characterized in that, The first dopant is selected from compounds with the following structural formulas:

8. The heterocyclic compound combination as described in claim 1, characterized in that, The second dopant is selected from compounds with the following structural formulas:

9. The heterocyclic compound combination as described in claim 1, characterized in that, It includes a hole transport layer compound, which is selected from the compounds shown in Formula 601 or Formula 602: X1, X2, X3, X4, and X5 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C5 alkyl, or substituted or unsubstituted C6-C20 aryl, wherein the substituent is hydrogen or deuterium.

10. The heterocyclic compound combination as described in claim 9, characterized in that, The hole transport layer compound is selected from compounds with the following structural formulas:

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, the organic layer comprising 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 of Formula 1 as described in claim 1, and the light-emitting layer contains the two-component host material as described in claim 1 and a dopant material.

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 as described in claim 9.

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