A compound, a plurality of host material compositions, and an organic electroluminescence device

Abstract

This invention provides a compound, various host material compositions, and an organic electroluminescent device. In the N-type material structure of this invention, the phenylene groups of the bridged triazine and 12H-benzothiophene[2,3-A]carbazole groups are connected to the N-phase with a common electron, resulting in relatively high activity. Replacing hydrogen atoms with deuterium atoms effectively improves the material's stability and thus its lifetime. The N-type material of this invention can form a good premix material with the P-type compound of this invention, exhibiting good P / N stability and mass production stability during evaporation. Furthermore, the formed premix material has a more balanced carrier mobility, thereby significantly improving the device's efficiency and lifetime.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescence technology, and more particularly to a compound, a combination of various host materials, and an organic electroluminescent device. Background Technology

[0002] Organic electroluminescence, generally speaking, refers to organic light-emitting diodes (OLEDs) that emit light by driving an organic semiconductor thin film with an electric current, thereby achieving the purpose of display.

[0003] Organic light-emitting diodes (OLEDs) consist of a cathode, an anode, and an organic layer sandwiched between them. Currently, industrially used OLED devices typically have a multi-layered organic structure, including layers such as a hole injection layer, a hole transport layer / electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. In OLED devices containing these layers, applying a voltage between the two electrodes causes holes to be injected into the organic layer from the anode and electrons to be injected from the cathode. When holes and electrons meet, excitons are formed. These excitons transfer energy to the doped material, and light is emitted through radiative transitions within the doped material.

[0004] In existing OLED devices, the poor compatibility between green light-emitting substrates leads to inefficient energy transfer to the doped materials, resulting in decreased efficiency. Furthermore, the lack of deuteration at active sites and high electron density sites in the material molecules results in poor chemical, thermal, and photoelectric stability, thus affecting device lifespan. Additionally, the P / N ratio of the green light-emitting substrate changes significantly with evaporation time, leading to large performance fluctuations, poor stability, and low yield.

[0005] The premix materials formed by combining N-type and P-type compounds of the present invention exhibit good thermal, chemical, and photoelectric stability because both compounds undergo deuteration at their respective active sites. Furthermore, the premix materials formed by the compounds of the present invention possess balanced carrier mobility, further broadening the exciton recombination region and thereby improving device lifetime and efficiency. Summary of the Invention

[0006] The purpose of this invention is to disclose, based on the prior art, a compound, a combination of various host materials, and an organic electroluminescent device.

[0007] To achieve the above objectives, the present invention provides a compound, the structural formula of which is represented by Formula 1:

[0008] In Equation 1, Y is O, S, or N-L3-Ar3. Ar1 and Ar2 are each independently selected from the following groups, either substituted or unsubstituted: phenyl, biphenyl, naphthyl, anthracene, dibenzofuranyl, dibenzothiophene, fluorenyl, phenanthrene, or benzophenanthrenefuranyl, wherein the substituent is selected from one or more of deuterium, fluorine, cyano, methyl, ethyl, tert-butyl, aryl (C6-C25), and heteroaryl (C3-C26); Ar3 is selected from the following groups, substituted or unsubstituted: phenyl, biphenyl, naphthyl or anthracene, wherein the substituent is selected from one or more of deuterium, fluorine, cyano, methyl, ethyl, tert-butyl, C6-C25 aryl, and C3-C26 heteroaryl; L1-L3 are each independently selected from the following groups, either directly bonded, substituted, or unsubstituted: aryl (C6-C18) or heteroaryl (C3-C20), wherein the substituent is selected from one or more of deuterium, fluorine, cyano, methyl, ethyl, tert-butyl, phenyl, pyridyl, and pyrimidinyl. R1-R 10 Each is independently selected from one or more of hydrogen, deuterium, fluorine, cyano, phenyl, biphenyl, C1-C6 alkyl, and C3-C8 cycloalkyl.

[0009] Preferably, Ar1 and Ar2 are each independently selected from substituted or unsubstituted groups of the following: phenyl, biphenyl, naphthyl or anthracene, wherein the substituent is selected from one or more of deuterium, fluorine, cyano, methyl, ethyl, tert-butyl, and C6-C18 aryl. Ar3 is selected from the following groups, substituted or unsubstituted: phenyl, biphenyl, naphthyl or anthracene, wherein the substituent is selected from one or more of deuterium, fluorine, cyano, methyl, ethyl, tert-butyl, and C6-C18 aryl; L1-L3 are each independently selected from C6-C18 aryl groups that are directly bonded or substituted or unsubstituted, wherein the substituents are selected from one or more of fluorine, deuterium, cyano, methyl, ethyl, tert-butyl, and phenyl. R1-R 10 Each is independently selected from one or more of hydrogen, deuterium, fluorine, cyano, phenyl, biphenyl, methyl, ethyl, tert-butyl, cyclopentyl, and cyclohexyl.

[0010] Preferably, Ar1 and Ar2 are each independently selected from the following groups, either substituted or unsubstituted: phenyl, biphenyl or naphthyl, wherein the substituent is selected from one or more of deuterium, fluorine, cyano, methyl, tert-butyl, phenyl, and biphenyl; Ar3 is selected from the following groups, substituted or unsubstituted: phenyl or biphenyl, wherein the substituent is selected from one or more of deuterium, fluorine, cyano, methyl, tert-butyl, phenyl, and biphenyl; L1-L3 are each independently selected from the following groups, either directly bonded, substituted, or unsubstituted: phenyl or biphenyl, wherein the substituent is selected from one or more of fluorine, deuterium, cyano, methyl, tert-butyl, and phenyl; R1-R 10 Each is independently selected from one or more of hydrogen, deuterium, fluorine, cyano, phenyl, biphenyl, methyl, and tert-butyl.

[0011] Preferably, Ar1 and Ar2 are each independently selected from the following groups, either substituted or unsubstituted: phenyl or biphenyl, wherein the substituent is selected from one or more of fluorine, deuterium, methyl, tert-butyl, and phenyl; Ar3 is selected from the following substituted or unsubstituted groups: phenyl or biphenyl, wherein the substituent is selected from one or more of deuterium, fluorine, methyl, tert-butyl, and phenyl; L1-L3 are each independently selected from the following groups, either directly bonded, substituted, or unsubstituted: phenyl or biphenyl, wherein the substituent is selected from one or more of fluorine, deuterium, methyl, and phenyl; R1-R 10 Each is independently selected from one or more of hydrogen, deuterium, fluorine, methyl, tert-butyl, and phenyl.

[0012] Preferably, Ar1 and Ar2 are each independently selected from the following groups, either substituted or unsubstituted: phenyl or biphenyl, wherein the substituent is selected from one or more of deuterium, methyl, and phenyl; Ar3 is selected from the following groups, substituted or unsubstituted: phenyl or biphenyl, wherein the substituent is selected from one or more of deuterium and phenyl; L1-L3 are each independently selected from one or more of the following: direct bond, phenyl, deuterated phenyl, biphenyl, and deuterated biphenyl; R1-R 10 Each is independently selected from one or more of hydrogen, deuterium, methyl, tert-butyl, and phenyl.

[0013] In a preferred embodiment, the compound of the present invention is any one of the following compounds: .

[0014] A composition of multiple host materials comprising a first host material and a second host material, wherein the first host material comprises a compound represented by Formula 1, and the second host material comprises a compound represented by any one or more of Formula 2 or Formula 3.

[0015] A 20 -A 29 Each is independently selected from hydrogen, deuterium, fluorine, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; L 21 and L 22 Each aryl group is independently selected from single-bonded, substituted, or unsubstituted C6-30; Ar 21 and Ar 22 Each is independently selected from substituted or unsubstituted C6-30 aryl groups and substituted or unsubstituted C3-30 heteroaryl groups;

[0016] L 31 and L 32 Each aryl group is independently selected from single-bonded, substituted, or unsubstituted C6-30; Ar 31 and Ar 32 Each is independently selected from substituted or unsubstituted C6-30 aryl groups and substituted or unsubstituted C3-30 heteroaryl groups; R 31 and R 32 Each is independently selected from hydrogen, deuterium, fluorine, cyano, C1-C10 alkyl, C1-C10 deuterated alkyl, C6-C30 aryl, C6-C30 deuterated aryl, C5-C30 heteroaryl, and C5-C30 deuterated heteroaryl. a 31 and a 32 Integers between 0 and 7.

[0017] Furthermore, the second host material is any one or more of the following compounds: .

[0018] An organic electroluminescent device includes a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode; wherein the organic layer contains the compound of the present invention.

[0019] Furthermore, the organic layer comprises a hole injection layer, a hole transport layer, a second hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; at least one of the hole injection layer, hole transport layer, second hole transport layer, light-emitting layer, hole blocking layer, electron transport layer, and electron injection layer contains the compound of the present invention, and further, the light-emitting layer contains the compound of the present invention.

[0020] The compounds of the present invention can be applied to the above-mentioned electroluminescent devices, and the organic electroluminescent devices can be used in the manufacturing of electronic display devices or OLED lighting devices.

[0021] The room temperature described in this invention is 25±5℃.

[0022] As a further improvement of the present invention, compared with the prior art, the beneficial effects of the present invention are: This invention designs a novel class of organic electroluminescent materials, which possess the following excellent properties: 1. In the N-type material structure of this invention, the phenylene group bridging the triazine group and the 12H-benzothiopheno[2,3-A]carbazole group, due to its connection with the N phase which shares electrons, exhibits relatively high activity. Furthermore, the two groups are ortho-substituted on the phenylene group, increasing steric hindrance within the molecule, reducing exciton quenching, and effectively improving the device's luminous efficiency. Further substitution of the hydrogen atom on the phenylene group with deuterium effectively improves the material's stability, thereby extending its lifetime.

[0023] 2. The N-type material of the present invention can form a good premix material with the P-type compound of the present invention. It has good P / N stability and mass production stability during the evaporation process. Furthermore, the premix material formed has a more balanced carrier mobility, thereby significantly improving the efficiency and lifespan of the device.

[0024] 3. The compounds of the present invention have good solubility, which effectively reduces the preparation cost of materials and the cleaning cost of masks. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the structure of the organic electroluminescent device provided by the present invention; The numbers in the diagram represent: 1-anode, 2-hole injection layer, 3-hole transport layer, 4-second hole transport layer, 5-light-emitting layer, 6-hole blocking layer, 7-electron transport layer, 8-electron injection layer, 9-cathode; Figure 2 This is an HPLC chromatogram of compound 1 prepared in Example 1 of the present invention; Figure 3 The DSC spectrum of compound 1 prepared in Example 1 of this invention is shown below. Figure 3 It can be seen that the glass transition temperature (Tg) of compound 1 is 130.64℃; Figure 4 The TGA spectrum of compound 1 prepared in Example 1 of this invention is shown below. Figure 4 It can be seen that the thermogravimetric temperature Td is 452.50℃. Detailed Implementation

[0026] The present invention will now be described in detail with reference to the embodiments shown in the accompanying drawings. However, it should be noted that these embodiments are not intended to limit the present invention. Equivalent changes or substitutions in function, method, or structure made by those skilled in the art based on these embodiments are all within the scope of protection of the present invention.

[0027] As used herein, in “substituted or unsubstituted”, “substituted” means that at least one hydrogen atom of the substituent or compound is substituted by one of the following groups: hydrogen, deuterium, fluorine, cyano, C1-C10 alkyl, C1-C10 deuterated alkyl, C6-C30 aryl, C6-C30 deuterated aryl, C5-C30 heteroaryl, or C5-C30 deuterated heteroaryl. “Unsubstituted” means that the hydrogen atom is not replaced by another substituent and the hydrogen atom is retained.

[0028] In this invention, deuterium refers to a stable isotope of hydrogen, also known as heavy hydrogen, and its element symbol is D.

[0029] In this invention, 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.

[0030] In this article, "heteroaryl" refers to a heteroaryl group obtained by replacing one or more carbon atoms in the structure of "aryl" with one or more heteroatoms (such as N, O or S).

[0031] 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.

[0032] Example 1:

[0033] The synthesis method of compound 1 is as follows:

[0034] Under nitrogen protection, 12H-benzofurano[2,3-a]carbazole-D10 1-a (28.2 g, 0.1 mol, 1 eq), o-bromofluorobenzene-D4 1-b (17.8 g, 0.1 mol, 1 eq), DMF 280 ml, and cesium carbonate (97.7 g, 0.3 mol, 3 eq) were added to the reaction flask. After the addition was complete, the reaction solution was refluxed for 12 h. The reaction was detected by HPLC. After cooling, 500 ml of water was added for washing, and the mixture was filtered. The filter cake was dried and purified by column chromatography using a petroleum ether / dichloromethane system, yielding approximately 37.4 g of intermediate 1-c, with a yield of 85%.

[0035] Under nitrogen protection, intermediate 1-c (37.4 g, 0.085 mol, 1 eq) was added to the reaction flask, followed by 400 ml of ultra-dry tetrahydrofuran. The mixture was cooled to -78 °C, and 2.5 M n-butyllithium (35.7 ml, 0.089 mol, 1.05 eq) was added dropwise. After the addition was complete, the mixture was kept at this temperature for 1 h. Triisopropyl borate (19.17 g, 0.102 mol, 1.2 eq) was then added dropwise. After the addition was complete, the mixture was allowed to rise naturally to room temperature, and a saturated ammonium chloride aqueous solution was added. The mixture was separated, and the organic phase was concentrated to dryness. Recrystallization from ethyl acetate yielded approximately 28.6 g of intermediate 1-d, with a yield of 83%.

[0036]

[0037] Under nitrogen protection, intermediate 1-d (28.6 g, 0.07 mol, 1 eq), triazine compound 1-f (24.1 g, 0.07 mol, 1 eq), toluene (300 ml), ethanol (150 ml), potassium carbonate (24.15 g, 0.175 mol, 2.5 eq), and Pd(PPh3)4 (0.8 g, 0.0007 mol, 1%) were added to the reaction flask. After the addition was complete, the reaction solution was heated to reflux and reacted overnight. The reaction was detected by HPLC. After the reaction solution was cooled, it was washed with water, separated, and the organic phase was passed through silica gel and concentrated to dryness. Column chromatography was performed to obtain approximately 27.2 g of compound 1, with a yield of 58%.

[0038] Compounds 2, 5, 6, 11, 12, 17, 18, 25, 26, 37, 38, 53, 54, 57, and 58 were obtained in a similar manner. Table 1-1

[0039] Table 1-2

[0040] Table 1-3

[0041] Table 1-4 .

[0042] Thermodynamic performance testing The thermogravimetric temperature Td and glass transition temperature Tg of compounds 1, 2, 5, 6, 11, 12, 17, 18, 25, 26, 37, 38, 53, 54, 57, and 58 in Examples 1-16 of this invention were tested, and the results are shown in Table 2. Note: The thermogravimetric temperature Td is the temperature at which 5% weight is lost in a nitrogen atmosphere. It is measured on a TGA N-1000 thermogravimetric analyzer with a nitrogen flow rate of 10 mL / min. The glass transition temperature Tg is measured by differential scanning calorimetry (DSC, Shinco DSC N-650) at a heating rate of 10℃ / min.

[0043] Table 2:

[0044] As shown in Table 2 above, the compounds of the present invention have high Td and Tg values, indicating that they have excellent thermal stability. When applied to organic electroluminescent devices, they can effectively extend the service life of organic electroluminescent devices and achieve better performance.

[0045] Device performance testing: Application Example 1: ITO was used as the anode substrate material for the reflective layer, and its surface was treated sequentially with water, acetone, and N2 ions. A 10 nm layer of HT-1 doped with 3% NDP-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 evaporated on top of the hole injection layer (HIL) to form a hole transport layer (HTL). 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 GPL evaporation, the emissive layer (EML) of the OLED light-emitting device is fabricated. Compound 1 and compound P-21 of the present invention are used as host materials GH-1 and GH-2, SP-1 is used as sensitizer, and compound GD-1 is used as dopant. The mass ratio of GH-1, GH-2, SP-1 and compound GD-1 is 66.5:30:3:0.5, and the thickness of the emissive layer is 30 nm. HB-1 was deposited onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm. 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. 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. 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.

[0046]

[0047]

[0048] Application Example 2-20 Compound 1 in Application Example 1 was replaced with compounds 2, 5, 6, 11, 12, 17, 18, 25, 26, 37, 38, 53, 54, 57, and 58 from Examples 2-16 of the present invention, while the other parts were the same as in Application Example 1. Based on this, organic electroluminescent devices of Application Examples 2-16 were fabricated.

[0049] Compound P-21 in Application Example 1 was replaced with compounds P-8, P-22, P-24, and P-79 from the present invention, respectively, while the rest remained the same as in Application Example 1. Based on this, organic electroluminescent devices of Application Examples 17-20 were fabricated.

[0050] Compare with Examples 1-4

[0051] The difference between Comparative Examples 1-4 and Application Example 1 is that compounds D1 and D2 from US20230180604A1, compound D3 from US20220029108A1, and compound D4 from KR1020230000949A are used to replace compound 1 in Application Example 1, respectively. The rest is the same as Application Example 1.

[0052] Organic electroluminescent devices prepared in Application Examples 1-20 and Control Examples 1-4 were tested respectively, and the test results are shown in Table 3.

[0053] Table 3

[0054] As shown in Table 3 above, applying the compounds of the present invention to organic electroluminescent devices as the main material can improve the luminous efficiency of organic electroluminescent devices to a certain extent, and reduce the start-up voltage and power consumption.

[0055] The organic electroluminescent devices prepared in Comparative Examples 1-4 and Application Examples 1-10, 17, and 18 were subjected to luminescence lifetime tests to obtain the luminescence 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 luminescent device lifetime testing system. The results are shown in Table 4. Table 4

[0056] As shown in Table 4 above, when the compound of the present invention is used as the main material of the light-emitting layer in organic electroluminescent devices, the service life of the prepared organic electroluminescent devices is greatly improved, so it has a very broad application prospect.

[0057] The detailed descriptions listed above are merely specific descriptions of feasible embodiments of the present invention, and are not intended to limit the scope of protection of the present invention. All equivalent embodiments or modifications made without departing from the spirit of the present invention should be included within the scope of protection of the present invention.

Claims

1. A compound, characterized in that, The compound is any one of the following compounds: 。 2. A multi-body material combination, comprising a first body material and a second body material, characterized in that, The first host material comprises a compound represented by Formula 1 as claimed in claim 1, and the second host material comprises a compound represented by any one or more of Formula 2 or Formula 3. ； A 20 -A 29 each independently selected from hydrogen, deuterium, fluorine, cyano, substituted or unsubstituted C1-C10alkyl, substituted or unsubstituted C1-C10cycloalkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl; L 21 and L 22 each independently is selected from a single bond, substituted or unsubstituted C6-30aryl; Ar 21 and Ar 22 each independently selected from substituted or unsubstituted C6-30aryl, substituted or unsubstituted C3-C30heteroaryl; ； L 31 and L 32 each independently is selected from a single bond, substituted or unsubstituted C6-30aryl; Ar 31 and Ar 32 Each is independently selected from substituted or unsubstituted C6-30 aryl groups and substituted or unsubstituted C3-30 heteroaryl groups; R 31 and R 32 Each is independently selected from hydrogen, deuterium, fluorine, cyano, C1-C10 alkyl, C1-C10 deuterated alkyl, C6-C30 aryl, C6-C30 deuterated aryl, C5-C30 heteroaryl, and C5-C30 deuterated heteroaryl. a 31 and a 32 Integers between 0 and 7; In Formulas 2 and 3, the substituents in the substituted C1-C10 alkyl groups, substituted C1-C10 cycloalkyl groups, substituted C6-C30 aryl groups, and substituted C3-C30 heteroaryl groups are each independently selected from hydrogen, deuterium, fluorine, cyano, C1-C10 alkyl groups, and C1-C10 deuterated alkyl groups.

3. The composition according to claim 2, characterized in that, The second host material is any one or more of the following compounds: 。 4. An organic electroluminescent device containing the material of claim 1, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer contains an organic electroluminescent compound as described in any one of claims 1.

5. The organic electroluminescent device according to claim 4, characterized in that, The organic layer comprises a hole injection layer, a hole transport layer, a second hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; at least one of the hole injection layer, hole transport layer, second hole transport layer, light-emitting layer, hole blocking layer, electron transport layer, and electron injection layer contains an organic electroluminescent compound as described in any one of claims 1.

6. The organic electroluminescent device according to claim 5, characterized in that, The light-emitting layer contains an organic electroluminescent compound as described in any one of claims 1.

7. The organic electroluminescent device according to claim 5, characterized in that, The compound of the present invention is applied in the organic electroluminescent device, which is used in the manufacture of electronic display devices or OLED lighting devices.

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