A triazine-containing heterocyclic compound, an organic electroluminescent device, and a display apparatus
By designing triazine-containing heterocyclic compounds as OLED electron transport materials, the shortcomings of existing materials in terms of driving voltage, current efficiency, and lifetime have been overcome, realizing OLED devices with low voltage, high efficiency, and long lifetime.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- FUYANG SINEVA MATERIAL TECHNOLOGY CO LTD
- Filing Date
- 2025-05-27
- Publication Date
- 2026-06-16
AI Technical Summary
Existing OLED materials have shortcomings in terms of driving voltage, current efficiency, and lifespan, making it difficult to meet the requirements of high-performance displays.
Triazine-containing heterocyclic compounds are used as electron transport materials. By fusion of indene rings and benzofuran-pyridine rings at specific positions, and combining triazine groups and other groups, the electron transport capability is improved and the electron injection transport barrier is reduced.
The driving voltage was reduced, the current efficiency was improved, and the lifespan of organic electroluminescent devices was extended.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic optoelectronic technology, specifically relating to a triazine-containing heterocyclic compound, an organic electroluminescent device, and a display device. Background Technology
[0002] Organic electroluminescent (OLED) materials have significant research value and promising application prospects in fields such as information display materials and organic optoelectronic materials. With the development of multimedia information technology, the performance requirements for flat panel display devices are becoming increasingly stringent. Currently, the main display technologies include plasma display devices, field emission display devices, and OLED devices. Among them, OLED devices possess a series of advantages such as self-illumination, low-voltage DC drive, all-solid-state operation, wide viewing angle, and rich colors. Compared with liquid crystal displays (LCDs), OLED devices do not require a backlight, have a wider viewing angle, lower power consumption, and a response speed 1000 times faster than LCDs. Therefore, OLED devices have a broader application prospect.
[0003] As OLED products gradually enter the market, people have increasingly higher requirements for their performance. The selection of materials for the hole layer, emissive layer, and other organic functional layers has a significant impact on the current efficiency, driving voltage, and lifetime of OLED devices. Currently, the exploration of functional layer materials with higher performance is still ongoing. Therefore, in order to meet people's higher requirements for OLED devices, there is an urgent need in this field to develop more types and higher performance OLED materials. Summary of the Invention
[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide a triazine-containing heterocyclic compound, an organic electroluminescent device, and a display device. The triazine-containing heterocyclic compound can be used as an electron transport material for OLED devices, and the resulting organic electroluminescent device has a lower driving voltage, higher current efficiency, and longer lifespan.
[0005] To achieve this objective, the present invention adopts the following technical solution:
[0006] In a first aspect, the present invention provides a triazine-containing heterocyclic compound having a structure as shown in Formula I:
[0007]
[0008] In Formula I, R1 and R2 are each independently selected from substituted or unsubstituted C6~C6. 30 aryl or substituted or unsubstituted C6-C 30 Mixed aromatics;
[0009] Ar1 is selected from single bonds, substituted or unsubstituted C6 to C1. 30aryl or substituted or unsubstituted C6-C 30 heteroaryl;
[0010] In R1, R2, and Ar1, the substituents are each independently selected from deuterium, F, cyano, trimethylsilyl, C1-C6 alkyl, C6 ... 30 Aryl or C3~C 30 Mixed aromatic compounds.
[0011] Preferably, the hydrogen atoms in Formula I can be independently replaced by deuterium, F, cyano, C1-C6 alkyl, C6-C6 alkyl, or C6-C6 alkyl. 30 Aryl or C6~C 30 heteroaryl substitution.
[0012] Preferably, C6~C 30 The aryl group is selected from phenyl, diphenyl, terphenyl, naphthyl, anthracene, indyl, fluorenyl, perylene, phenanthryl, pyrene, fluoranyl, spirofluorenyl, triphenylene, benzo[fluorenyl], dibenzo[fluorenyl], naphthyl[fluorenyl], and benzo[phenanthryl].
[0013] Preferably, C6~C 30 The arylene group is selected from phenylene, diphenylene, terphenylene, naphthylene, anthracene, indene, fluorene, perylene, phenanthrene, pyrene, fluorenylene, spirofluorene, tricrene, benzo[a]fluorene, dibenzo[a]fluorene, naphthylfluorene, and benzo[a]phenanthrene.
[0014] Preferably, the C1 to C6 alkyl group is selected from methyl, ethyl, propyl, butyl, pentyl, or hexyl.
[0015] Preferably, C6~C 30 heteroaryl, C3~C 30 heteroaryl, C6-C 30 The heteroatoms in the heteroaryl group are each independently selected from O, S, or N.
[0016] Preferably, C6~C 30 The heteroaryl group is selected from carbazolyl, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, dibenzofuranophenyl, or dibenzothiophenophenyl.
[0017] Preferably, C3 to C 30 The heteroaryl group is selected from triazinyl, carbazolyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuranophenyl, or dibenzothiophenophenyl.
[0018] Preferably, C6~C 30The heteroaryl group is selected from imidazolyl, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, dibenzofuranophenyl, or dibenzothiophene.
[0019] Preferably, in Formula I, R1 and R2 are each independently selected from phenyl, diphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, 9,9-dimethylfluorenyl, fluoranyl, triphenylene, phenanthryl, carbazole, N-phenylcarbazole, N-carbazolephenyl, dibenzofuranyl, or dibenzothiazolyl; more preferably, in Formula I, R1 and R2 are each independently selected from phenyl, diphenyl, naphthyl, phenylnaphthyl, 9,9-dimethylfluorenyl, carbazole, or dibenzofuranyl.
[0020] Preferably, in Formula I, Ar1 is selected from single bonds, phenylene, diphenylene, or naphthylene.
[0021] Preferably, the triazine-containing heterocyclic compound is selected from any one of the following compounds:
[0022]
[0023]
[0024]
[0025]
[0026]
[0027]
[0028] Preferably, the triazine-containing heterocyclic compound is selected from any one of compounds 1 to 12:
[0029]
[0030] This invention lists some specific structural forms of the triazine-containing heterocyclic compounds, but the triazine-containing heterocyclic compounds of this invention are not limited to these listed chemical structures. Any structure based on the structure shown in Formula I, where R1, R2, and Ar1 satisfy the above-mentioned limiting conditions should be included.
[0031] In a second aspect, the present invention provides an organic electroluminescent device comprising a triazine-containing heterocyclic compound as described in the first aspect.
[0032] Preferably, the organic electroluminescent device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode;
[0033] The organic layer includes triazine-containing heterocyclic compounds as described in the first aspect.
[0034] Preferably, the organic layer includes an electron transport layer;
[0035] The electron transport layer comprises a triazine-containing heterocyclic compound as described in the first aspect.
[0036] Thirdly, the present invention provides a display device, the display device comprising the aforementioned organic electroluminescent device.
[0037] Compared with the prior art, the present invention has the following beneficial effects:
[0038] The triazine-containing heterocyclic compound provided by this invention has a high conjugation ability due to the fusion of the indene ring and the benzofuran-pyridine ring at specific positions. Furthermore, by combining the triazine group linked at specific positions with other groups defining specific positions in the parent core, it can increase the electron transport capability of the device, reduce the electron injection transport barrier, lower the driving voltage, and thus improve the luminous efficiency of the device. It exhibits excellent luminescent performance and can be used to prepare organic electroluminescent devices, especially as an electron transport layer material in organic electroluminescent devices, effectively reducing the driving voltage, improving current efficiency, and extending the service life of organic electroluminescent devices. Detailed Implementation
[0039] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.
[0040] Synthesis Example 1
[0041] This embodiment provides a method for synthesizing compound 1, and the synthetic route of compound 1 is as follows:
[0042]
[0043] Synthesis of intermediate 1-1
[0044] Under nitrogen protection, 20.0 mmol of raw material A, 20.0 mmol of raw material B, 300 ml of toluene, and 0.04 mol of glacial acetic acid were added to the reaction flask. The mixture was heated to reflux and stirred for 6 h. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography using ethyl acetate / n-heptane as the eluent to obtain intermediate 1-1.
[0045] The intermediate 1-1 was analyzed by mass spectrometry, and the m / z was 401.14.
[0046] Synthesis of intermediates 1-2
[0047] According to the synthetic method disclosed in Org. Lett., 2021, 23, 9526-9532, under nitrogen protection, 30.0 mmol of intermediate 1-1 and 34.0 mmol of starting material C were dissolved in 100 mL of 1,2-dichloroethane, and then 60.0 mmol of trifluoromethanesulfonic acid was added. The mixture was heated in an oil bath at 80 °C and stirred for 10 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated and dried under reduced pressure, and purified by silica gel column chromatography to obtain intermediate 1-2.
[0048] Intermediates 1-2 were analyzed by mass spectrometry, and the m / z was 381.15.
[0049] Synthesis of intermediates 1-3
[0050] Under nitrogen protection, 30.0 mmol of intermediate 1-2, 120.0 mmol of anhydrous potassium carbonate and 90 mL of LDM were mixed, heated to 125 °C, and stirred for 5 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 250 mL of ice water, filtered, and the filter cake was washed with water and then recrystallized with methanol to obtain intermediate 1-3.
[0051] Intermediates 1-3 were analyzed by mass spectrometry, and the m / z was 361.15.
[0052] Synthesis of intermediates 1-4
[0053] Under nitrogen protection, 20.0 mmol of intermediate 1-3 was dissolved in 100 mL of dichloromethane, and then 22.0 mmol of N-bromosuccinimide was added in portions. The mixture was stirred at room temperature for 2 h. After the reaction was completed, 50 mL of water was added, the mixture was separated, the organic phase was washed three times with water, dried, filtered, and the filtrate was concentrated and dried under reduced pressure to obtain intermediate 1-4.
[0054] Mass spectrometry analysis was performed on intermediates 1-4, and the m / z was 439.06.
[0055] NMR analysis of intermediates 1-4 yielded the following data: 1 H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ8.11 (d, 1H), δ8.09 (m, 1H), 7.55 (m, 1H), δ7.53–7.39 (m, 7H), δ7.35 (d, 1H), δ7.20 (m, 1H), δ1.71 (s, 6H).
[0056] Synthesis of intermediates 1-5
[0057] Under nitrogen protection, 20.0 mmol of intermediate 1-4, 30 mmol of pinacol diborate, 0.4 mmol of bis(triphenylphosphine)palladium dichloride, 60 mmol of potassium acetate, and 200 ml of toluene were added to a reaction flask. The mixture was heated to reflux and stirred for 6 h. After the reaction was completed, the mixture was cooled to room temperature, and 400 ml of water was added to the reaction solution. The mixture was stirred for 30 min, and the solution was separated. The obtained organic phase was washed twice with 300 ml of water. The organic phase was then concentrated to 100 ml, and 200 ml of ethanol was added. The mixture was stirred for 30 min, filtered, and the filter cake was recrystallized with a mixed solvent of toluene and ethanol to obtain intermediate 1-5.
[0058] Mass spectrometry analysis was performed on intermediates 1-5, and the m / z was 487.23.
[0059] Synthesis of Compound 1
[0060] Under nitrogen protection, 20.0 mmol of starting material D (2-chloro-4,6-diphenyl-1,3,5-triazine), 22.0 mmol of intermediate 1-5, 0.4 mmol of tetra-triphenylphosphine palladium, 30 mmol of potassium carbonate, 300 ml of toluene, 100 ml of ethanol, and 100 ml of water were added to a reaction flask. The mixture was heated to reflux and stirred for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and 400 ml of ethanol was added to the reaction solution. The mixture was stirred for 30 min, filtered, and the filter cake was washed twice with 300 ml of water. The filter cake was then filtered again and recrystallized from the filter cake using a mixed solvent of toluene and ethanol to obtain compound 1.
[0061] Compound 1 was analyzed by mass spectrometry, and the m / z was 592.23.
[0062] Following the synthetic method of compound 1 described above, compounds as shown in Table 1 were prepared, differing only in that starting material D was replaced with an equimolar amount of other compounds (see Table 1), while other conditions remained unchanged:
[0063] Table 1
[0064]
[0065]
[0066]
[0067]
[0068] For other compounds whose specific synthesis methods are not listed, they can be synthesized by referring to the above examples and combining them with common knowledge in the field.
[0069] The specific structures of some of the materials used in the following device embodiments and device comparison examples are as follows:
[0070]
[0071] The device embodiments use compounds from this application as electron transport materials in organic electroluminescent devices, while the device comparative examples use E1 to E3 as electron transport materials in organic electroluminescent devices.
[0072] Device Example 1
[0073] The structure of the organic electroluminescent device is: ITO / HT (40nm) / BH-1:BD-13% (30nm) / Compound 1 (30nm) / LiF (0.5nm) / Al (150nm).
[0074] The fabrication method of the above-mentioned organic electroluminescent device is as follows:
[0075] The glass substrate coated with an ITO transparent conductive layer (as the anode) was ultrasonically treated in a cleaning agent, then rinsed in deionized water, then ultrasonically degreased in a mixed solvent of acetone and ethanol, then baked in a clean environment until completely dehydrated, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam to improve the surface properties and enhance the bonding ability with the hole injection layer.
[0076] The glass substrate was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁶. -5 ~1×10 -6 Pa, HT is vacuum-deposited on the anode as a hole transport layer at a deposition rate of 0.1 nm / s and a film thickness of 40 nm;
[0077] A light-emitting layer is vacuum-deposited on top of the hole transport layer at a deposition rate of 0.1 nm / s and a film thickness of 30 nm. The main material of the light-emitting layer is BH-1, and the doping material is BD-1. The 3% refers to the doping ratio of the doping material, that is, the volume ratio of the main material of the light-emitting layer to the doping material is 97:3.
[0078] Compound 1 was vacuum-deposited as an electron transport layer on top of the luminescent layer at a deposition rate of 0.1 nm / s, resulting in a film thickness of 30 nm. 0.5 nm of LiF and 150 nm of Al were then vacuum-deposited on the electron transport layer as an electron injection layer and a cathode, respectively. The brightness, driving voltage, current efficiency, and lifetime of the fabricated organic electroluminescent device were measured.
[0079] Device Examples 2-12
[0080] Device Examples 2 to 12 each provide an organic electroluminescent device, which differs from Device Example 1 only in that the electron transport material is different (see Table 2 below), while other conditions are the same as those in Device Example 1.
[0081] Device Comparison Examples 1-3
[0082] Comparative Examples 1 to 3 each provide an organic electroluminescent device, which differs from Device Example 1 only in that the electron transport material is different (see Table 2 below), while other conditions are the same as Device Example 1.
[0083] Performance testing
[0084] Test Method: The driving voltage, current efficiency, and lifetime LT90 of the OLED devices provided above were tested. LT90 refers to the time required for the brightness to decrease to 90% of its original brightness while maintaining an initial brightness of 1000 nits at a constant current density. Test items included the brightness, driving voltage, current efficiency, and lifetime LT90 of the organic light-emitting diode. The driving voltage, current efficiency, and LT90 data were all based on a brightness of 1000 cd / m². 2 The relative values at different times (based on device comparison example 1). The performance test results of the organic electroluminescent devices are shown in Table 2 below:
[0085] Table 2
[0086]
[0087] As shown in Table 2, this invention has obtained triazine-containing heterocyclic compounds through molecular design, which can be used as electron transport materials for OLED light-emitting devices, enabling OLED light-emitting devices to have lower driving voltage, higher current efficiency and longer lifespan.
[0088] The present invention has been illustrated with the above embodiments to describe the detailed process flow of the present invention. However, the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims
1. A triazine-containing heterocyclic compound, characterized in that, The triazine-containing heterocyclic compound has a structure as shown in Formula I: Formula I In Formula I, R1 and R2 are each independently selected from substituted or unsubstituted C6~C6. 30 aryl or substituted or unsubstituted C6~C 30 Mixed aromatics; Ar1 is selected from single bond, substituted or unsubstituted C6~C. 30 aryl groups, either substituted or unsubstituted, C6~C 30 heteroaryl; In R1, R2, and Ar1, the substituents are each independently selected from deuterium, F, cyano, trimethylsilyl, C1-C6 alkyl, C6 ... 30 Aryl or C3~C 30 Mixed aromatic compounds.
2. The triazine-containing heterocyclic compound according to claim 1, characterized in that, In Formula I, the hydrogen atoms can be independently replaced by deuterium, F, cyano, C1-C6 alkyl, C6-C6 alkyl, or C4-C6 alkyl groups. 30 Aryl or C6~C 30 heteroaryl substitution.
3. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized in that, The C6~C 30 The aryl group is selected from phenyl, diphenyl, terphenyl, naphthyl, anthracene, indyl, fluorenyl, perylene, phenanthryl, pyrene, fluoranyl, spirofluorenyl, triphenylene, benzo[fluorenyl], dibenzo[fluorenyl], naphthyl[fluorenyl], and benzo[phenanthryl].
4. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized in that, The C6~C 30 The arylene group is selected from phenylene, diphenylene, terphenylene, naphthylene, anthracene, indene, fluorene, perylene, phenanthrene, pyrene, fluorenylene, spirofluorene, tricrene, benzo[a]fluorene, dibenzo[a]fluorene, naphthylfluorene, and benzo[a]phenanthrene.
5. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized by The C1-C6 alkyl group is selected from methyl, ethyl, propyl, butyl, pentyl, or hexyl.
6. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized by The C6~C 30 heteroaryl, C3~C 30 heteroaryl, C6~C 30 The heteroatoms in the heteroaryl group are each independently selected from O, S, or N.
7. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized by The C6~C 30 The heteroaryl group is selected from carbazolyl, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, dibenzofuranophenyl, or dibenzothiophenophenyl.
8. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized by The C3~C 30 The heteroaryl group is selected from triazinyl, carbazolyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuranophenyl, or dibenzothiophenophenyl.
9. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized by The C6~C 30 The heteroaryl group is selected from imidazolyl, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, dibenzofuranophenyl, or dibenzothiophene.
10. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized by In Formula I, R1 and R2 are each independently selected from phenyl, diphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, 9,9-dimethylfluorenyl, fluoranyl, triphenylene, phenanthryl, carbazolyl, N-phenylcarbazolyl, N-carbazolylphenyl, dibenzofuranyl, or dibenzothiazolyl.
11. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized by Ar1 is selected from single bonds, phenylene, diphenylene, or naphthylene.
12. The triazine-containing heterocyclic compound according to claim 1 or 2, characterized by The triazine-containing heterocyclic compound is selected from any one of the following compounds: 。 13. An organic electroluminescent device, characterized by The organic electroluminescent device comprises a triazine-containing heterocyclic compound as described in any one of claims 1 to 12.
14. The organic electroluminescent device according to claim 13, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode; The organic layer includes the triazine-containing heterocyclic compound.
15. The organic electroluminescent device according to claim 14, characterized in that The organic layer includes an electron transport layer; The electron transport layer comprises the triazine-containing heterocyclic compound.
16. A display device comprising: The display device includes the organic electroluminescent device according to any one of claims 13 to 15.