Triazine compound, OLED (Organic Light Emitting Diode) with same and organic light emitting device

Abstract

The invention relates to the technical field of organic photoelectric materials, in particular to a triazine compound, an OLED with the compound and an organic light-emitting device with the compound. According to the triazine compound disclosed by the invention, a triazine structure is taken as a core, and aryl and alkyl are combined with a fluorenyl group to form side chain matching, so that the compound has excellent luminous efficiency and relatively good thermal stability; meanwhile, when the triazine compound provided by the invention acts on a device, the organic light-emitting device can effectively have lower driving voltage and maintain the stability of the voltage, the light-emitting efficiency is improved, the service life is obviously prolonged, and the triazine compound has a very good application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of organic photoelectric material preparation, and in particular to a triazine compound, an OLED having the compound, and an organic light-emitting device. Background Art

[0002] Organic light-emitting diodes (OLEDs), also known as organic electroluminescent devices, are a technology that applies voltage to organic electroluminescent elements to inject holes from the anode and electrons from the cathode into the light-emitting layer respectively. The injected holes and electrons recombine to form excitons, resulting in luminescence. It can convert electrical energy into light energy through organic light-emitting materials.

[0003] In organic electroluminescent devices, since the carrier migration speed of holes in most materials does not match that of electrons, the two carriers are unlikely to recombine in the light-emitting layer, which will lead to a decrease in the photoelectric performance of the device, and an increase in leakage current, causing the device to heat up and reduce the device life. Existing materials are still insufficient in improving device performance. Even if different combinations of multiple materials are used, display technology still has problems such as high driving voltage and short display life, which seriously affects the further practical application of this technology.

[0004] Therefore, it is necessary to continue to work hard to develop organic light-emitting devices with low voltage drive, high brightness and long life, and to find suitable OLED optoelectronic functional materials for OLED devices to solve the above problems. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a triazine compound, an OLED having the compound, and a display or lighting device. The provided triarylamine compound has a triazine structure as the core, and an aryl group and an alkyl group are combined with a fluorenyl group to form a side chain, so that the triazine compound is used in an organic electroluminescent device, so that the device can have both high efficiency and long service life.

[0006] The triazine compound provided by the present invention is realized by the following technical scheme: A triazine compound having a structure shown in the following formula I: ; In formula I, R1, R2, R3, and R4 are each independently monosubstituted, disubstituted or substituted to the maximum number of substitutions; R1 and R2 are each independently selected from hydrogen, deuterium, cyano, cyano-substituted or unsubstituted C6-C30 aryl, and C5-C36 heteroaryl; L is independently selected from a single bond, deuterated or undeuterated C6-C30 arylene; R3 and R4 are each the same or different and are selected from substituted or unsubstituted C1-C24 alkyl, C3-C20 cycloalkyl; when R3 and R4 are substituted, the substituent is selected from one or more of deuterium and C6~C30 aryl, and the structure shown in formula I can be partially or fully deuterated.

[0007] Preferably, in the formula I, R1 and R2 are each independently selected from hydrogen, deuterium, cyano, cyano substituted or unsubstituted phenyl, cyano substituted or unsubstituted naphthyl, cyano substituted or unsubstituted phenanthrenyl, cyano substituted or unsubstituted naphthylphenyl, cyano substituted or unsubstituted biphenyl, and dibenzofuranyl.

[0008] Preferably, in the formula I, L is independently selected from a single bond, a deuterated or undeuterated phenylene group, a deuterated or undeuterated biphenylene group; R3 and R4 are each independently selected from a methyl group, an ethyl group, a propyl group, a tert-butyl group, a pentyl group, a phenylpropyl group, a diphenylethyl group, a tert-butyl group substituted with a phenyl group, and a cyclopentanyl group.

[0009] According to one or more embodiments, the present invention provides a triazine compound selected from any one of the chemical structures shown below, wherein D represents deuterium: .

[0010] The present invention also provides a use of the triazine compound described above in an organic electroluminescent device.

[0011] The present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising: substrate layer; a first electrode, the first electrode being on the substrate; An organic light-emitting functional layer, the organic light-emitting functional layer is on the first electrode; A second electrode, the second electrode being on the organic light-emitting functional layer; The organic light-emitting functional layer includes the triazine compound as described above.

[0012] Preferably, at least one of the organic light-emitting functional layers is an electron transport layer or a hole blocking layer, and the electron transport layer or the hole blocking layer comprises the triazine compound as described above.

[0013] The present invention also provides a composition, which comprises the triazine compound as described in Formula I.

[0014] The present invention also provides a preparation, which comprises a triazine compound having a structure as shown in the above formula I or a composition as described above and at least one solvent. The solvent is not particularly limited, and can be used as unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, butyl chloride, butyl bromide, pentyl chloride, pentyl bromide, hexyl chloride, hexyl bromide, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran, tetrahydropyran, and ester solvents such as alkyl benzoate.

[0015] The organic electroluminescent device of the present invention can be used in an OLED lighting or display device.

[0016] The present invention also provides a display or lighting device, which comprises one or more of the organic electroluminescent devices described above.

[0017] In summary, compared with the prior art, the present invention has the following beneficial effects: The triazine compounds of the present invention are composed of an aromatic group and an alkyl group combined with a fluorenyl group to form a side chain combination, so that the compounds have good thermal stability, excellent luminous efficiency and a good service life; at the same time, the triazine compounds provided by the present invention are used in devices, which can effectively make the organic light-emitting devices have a lower driving voltage and maintain voltage stability, and the luminous efficiency is improved, and the working life of the devices can also be better. DETAILED DESCRIPTION

[0018] The following will be described clearly and completely in conjunction with the technical solutions of the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0019] The aryl group of the present invention refers to a general term for a monovalent group after removing a hydrogen atom from the aromatic core carbon of an aromatic hydrocarbon molecule, which can be a monocyclic aryl group or a condensed ring aryl group. The aryl group can be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples may include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl, anthracenyl, phenanthrenyl or pyrenyl, but are not limited thereto. Aryl or aromatic group-as used herein, non-condensed and condensed systems are considered. The aryl group can be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, perylene and azulene, with preference given to phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl and m-quaterphenyl.

[0020] The heteroaryl group of the present invention refers to a general term for a group obtained by replacing one or more aromatic carbon atoms in an aromatic group with a heteroatom, wherein the heteroatom includes but is not limited to oxygen, sulfur, silicon or nitrogen atoms, and the heteroaryl group may be a monocyclic heteroaryl group or a condensed ring heteroaryl group, and may be a heteroaryl group having 6 to 30 carbon atoms, preferably a heteroaryl group having 6 to 20 carbon atoms. Examples may include pyridyl, pyrrolyl, pyridyl, thienyl, furanyl, indolyl, quinolyl, isoquinolyl, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, etc., but are not limited thereto.

[0021] The alkyl group of the present invention includes straight chain and branched chain alkyl groups. It can be an alkyl group having 1 to 24 carbon atoms, and preferably an alkyl group having 1 to 4 carbon atoms, including methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, etc. In addition, the alkyl group can be optionally substituted.

[0022] Cycloalkyl of the present invention refers to and includes monocyclic, polycyclic and spiroalkyl. Preferred cycloalkyl is a cycloalkyl containing 3 to 20 ring carbon atoms, more preferably a cycloalkyl containing 3 to 12 ring carbon atoms, and particularly preferably a cycloalkyl containing 3 to 6 ring carbon atoms, and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo [3.1.1] heptyl, spiro [4.5] decyl, spiro [5.5] undecyl, adamantyl, etc. In addition, the cycloalkyl may be optionally substituted.

[0023] Throughout the specification, unless explicitly described to the contrary, "comprising" any component will be understood to imply the inclusion of other elements, rather than excluding any other elements. In addition, it should be understood that throughout the specification, when an element such as a layer, film, region or substrate is referred to as being "on" or "above" another element, it can be "directly on" another element, or there may be intervening elements. In addition, "on..." or "above..." means being located above the target portion, and does not necessarily mean being located above according to the direction of gravity.

[0024] An object of the present invention is to provide an organic electroluminescent device, which includes: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; a second electrode, which is on the organic light-emitting functional layer; the organic light-emitting functional layer includes a hole blocking layer and an electron transport layer. In one embodiment of the present invention, the hole blocking layer or the electron transport layer in the organic electroluminescent (OLED) device contains one or more of the compounds shown in the above general formula I.

[0025] In a preferred embodiment of the present invention, an OLED is provided, which includes a substrate, an anode, a cathode, and an organic light-emitting functional layer, wherein the organic light-emitting functional layer may include a light-emitting layer, a light-emitting auxiliary layer, a hole transport layer, a hole injection layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., or may only include a light-emitting layer and one or more other layers; wherein the hole blocking layer or the electron transport layer may contain one or more of the compounds represented by the above general formula I. Optionally, there is a covering layer, a protective layer and / or an encapsulation layer on the organic light-emitting functional layer.

[0026] The substrate of the present invention can be any substrate used in a typical organic light-emitting device. It can be a glass or transparent plastic substrate, or a substrate of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, the use direction is different.

[0027] As materials for the hole injection layer, the hole transport layer, the electron injection layer, and the light emitting layer, any material can be selected from known related materials used for OLED devices.

[0028] The present invention is described in detail below in conjunction with specific examples. Synthesis Examples All raw materials and solvents are commercially available unless otherwise specified, and the solvents are used directly without further treatment.

[0029] Example

[0030] Example 1: Synthesis of Compound 7 Synthesis route: ; Synthesis method: 1) Add 7-1 (10 mmol), 7-2 (10 mmol), and 10 mL of dioxane: water (mass ratio 4:1) to the reaction bottle, mix, put into a 50 mL flask, and reflux for 24 hours. Cool to room temperature, then slowly add saturated MgSO4 aqueous solution and ethyl acetate to the solution for extraction three times, then remove the solvent from the organic layer by rotary evaporator, and obtain compound 7 by column chromatography; The structure of the test target product compound 7: LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 861.41, and the test value was 862.07.

[0031] Example 2: Synthesis of Compound 19 Referring to the synthesis steps and reaction conditions of Example 1, compound 19 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 937.44 and the test value was 938.16.

[0032] Example 3: Synthesis of Compound 42 Referring to the synthesis steps and reaction conditions of Example 1, compound 42 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 838.40 and the test value was 839.06.

[0033] Example 4: Synthesis of Compound 58 Referring to the synthesis steps and reaction conditions of Example 1, compound 58 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 861.41 and the test value was 862.11.

[0034] Example 5: Synthesis of Compound 92 Referring to the synthesis steps and reaction conditions of Example 1, compound 92 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 813.41 and the test value was 814.03.

[0035] Example 6: Synthesis of Compound 100 Compound 100 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was analyzed by liquid chromatography-mass spectrometry: the theoretical value was 711.36 and the test value was 711.92.

[0036] Example 7: Synthesis of Compound 109 Compound 109 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was analyzed by liquid chromatography-mass spectrometry: the theoretical value was 813.41 and the test value was 814.05.

[0037] Example 8: Synthesis of Compound 122 Referring to the synthesis steps and reaction conditions of Example 1, compound 122 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 961.44 and the test value was 962.20.

[0038] Example 9: Synthesis of Compound 124 Referring to the synthesis steps and reaction conditions of Example 1, compound 124 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 827.39 and the test value was 828.01.

[0039] Example 10: Synthesis of Compound 133 Referring to the synthesis steps and reaction conditions of Example 1, compound 133 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 805.35 and the test value was 805.97.

[0040] Example 11: Synthesis of Compound 144 Referring to the synthesis steps and reaction conditions of Example 1, compound 144 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 779.33 and the test value was 779.95.

[0041] Example 12: Synthesis of Compound 145 Referring to the synthesis steps and reaction conditions of Example 1, compound 145 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 909.41 and the test value was 910.03.

[0042] Example 13: Synthesis of Compound 158 Referring to the synthesis steps and reaction conditions of Example 1, compound 158 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 837.41 and the test value was 838.05.

[0043] Example 14: Synthesis of Compound 165 Referring to the synthesis steps and reaction conditions of Example 1, compound 165 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 875.50 and the test value was 876.18.

[0044] Example 15: Synthesis of Compound 168 Compound 168 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 821.46 and the test value was 822.10.

[0045] Several application examples of the triazine compounds of the present invention in OLED devices are listed below to further illustrate the beneficial effects of the compounds of the present invention. The materials used in the examples are purchased from commercial sources or synthesized by the user.

[0046] Fabrication of OLED devices: As a reference preparation method for a device embodiment, the present invention evaporates 50-500nm ITO / Ag / ITO on an alkali-free glass substrate as an anode, evaporates a hole injection layer (5nm-20nm), a hole transport layer (50-150nm), a light-emitting auxiliary layer (5-120nm), a light-emitting layer (20-50nm), a hole blocking layer (5-20nm), an electron transport layer (20-80nm), and an electron injection layer (1-10nm) on the anode, and then co-evaporates Mg and Ag (weight ratio 1:9, 10-50nm) to make a semi-transparent cathode, and then evaporates a cover layer compound. Finally, the light-emitting device is encapsulated using an epoxy resin adhesive in a nitrogen atmosphere.

[0047] In a preferred specific embodiment, the structure of the OLED device provided by the present invention is: first, use an ultrasonic cleaner to wash the alkali-free glass substrate with isopropanol for 15 minutes, and then perform UV ozone cleaning in the air for 30 minutes. The treated substrate is vacuum-deposited with ITO / Ag / ITO 100nm as an anode, and then a hole injection layer (HT:PD, 10nm, 2%), a hole transport layer (HT, 130nm), a light-emitting auxiliary layer (BP, 5nm), a blue light-emitting layer (main material: doping material = BH:BD (weight ratio 98:2, 30nm)), a hole blocking layer (compound 7, 5nm), an electron transport layer (ET:Liq=1:1, 30nm), and an electron injection layer (Yb, 1nm) are sequentially stacked and evaporated, and Mg and Ag (weight ratio 1:9, 14nm) are co-evaporated to make a semi-transparent cathode, and then a compound CPL (65nm) is evaporated as a covering layer. Finally, the light emitting device is encapsulated with epoxy resin adhesive in a nitrogen atmosphere, which is recorded as Application Example 1. The molecular structure formula of the relevant material is as follows (particularly preferably selected from the following structure, but it does not mean that the present invention is limited to the following structure): .

[0048] The method provided in the above-mentioned application example 1 was used to prepare application examples 2 to 15 and comparative example 1, the only difference being that the compounds listed in Table 1 were used as hole blocking materials to replace compound 7 in application example 1. The structure of Ref-1 used in the comparative example is as follows: .

[0049] Performance evaluation of OLED devices: The current of the OLED device at different voltages was tested using a Keithley 2365A digital nanovoltmeter, and the current was then divided by the luminous area to obtain the current density of the OLED device at different voltages. The brightness and radiant energy flux density of the OLED device at different voltages were tested using a Konicaminolta CS-2000 spectroradiometer. Based on the current density and brightness of the OLED device at different voltages, the current density (10 mA / cm 2 ) working voltage Volt and current efficiency (cd / A), BI=E / CIEy, refers to the Blue Index in blue light, and is also a parameter for measuring the luminous efficiency of blue light. E refers to the current efficiency, and CIEy refers to the vertical coordinate color point obtained by bringing the wavelength of the device's luminous half-peak width into the CIE1930 software. The test data is shown in Table 1.

[0050] Table 1 Application examples of hole blocking materials and their electronic luminescence properties

[0051] As can be seen from Table 1, compared with Comparative Example 1, Application Examples 1 to 15 have lower operating voltage, higher BI luminous efficiency and longer service life. The performance improvement of each application example is based on the fact that the triazine compound of the present invention has a dendritic molecule with a triazine structure as the core, and the nitrogen-containing heterocyclic ring has a strong electron-withdrawing ability and a large conjugated plane, so that the compound has good thermal stability and a high glass transition temperature, and the service life of the device is improved; at the same time, by combining the fluorene group with the alkyl group and the aromatic group, it can have a greater impact on the luminescent properties of the compound, thereby improving the luminous efficiency of the device, and can better achieve the balance of electron and hole transmission and the exciton conversion rate, and reduce the power consumption of the device.

[0052] This specific embodiment is merely an explanation of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed. However, as long as they are within the scope of the claims of the present invention, they are protected by the patent law.

Claims

1. A triazine compound, characterized in that: The triazine compound has a structure as shown in the following formula I: ； In formula I, R1, R2, R3, and R4 are each independently monosubstituted, disubstituted, or substituted to the maximum number of substitutions; R1 and R2 are each independently selected from hydrogen, deuterium, cyano, cyano-substituted or unsubstituted C6-C30 aryl, or C5-C36 heteroaryl; L is independently selected from a single bond, deuterated or undeuterated C6-C30 arylene; R3 and R4 are each the same or different and are selected from substituted or unsubstituted C1-C24 alkyl, or C3-C20 cycloalkyl; when R3 and R4 are substituted, the substitution is selected from one or more of deuterium and C6-C30 aryl, and the structure shown in formula I may be partially or fully deuterated.

2. The triazine compound according to claim 1, characterized in that In the formula I, R1 and R2 are each independently selected from hydrogen, deuterium, cyano, cyano-substituted or unsubstituted phenyl, cyano-substituted or unsubstituted naphthyl, cyano-substituted or unsubstituted phenanthryl, cyano-substituted or unsubstituted naphthylphenyl, cyano-substituted or unsubstituted biphenyl, and dibenzofuranyl.

3. The triazine compound according to claim 1, characterized in that: In the formula I, L is independently selected from a single bond, a deuterated or undeuterated phenylene group, a deuterated or undeuterated biphenylene group; R3 and R4 are each independently selected from a methyl group, an ethyl group, a propyl group, a tert-butyl group, a pentyl group, a phenylpropyl group, a diphenylethyl group, a tert-butyl group substituted with a phenyl group, and a cyclopentanyl group.

4. The triazine compound according to claim 1, characterized in that: The triazine compound is selected from any one of the following chemical structures, where D represents deuterium: 。 5. Use of the triazine compound according to any one of claims 1 to 4 in the preparation of an organic electroluminescent device.

6. A preparation, characterized in that The preparation comprises the triazine compound according to any one of claims 1 to 4 and at least one solvent.

7. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises: substrate layer; a first electrode, the first electrode being on the substrate; An organic light-emitting functional layer, the organic light-emitting functional layer is on the first electrode; A second electrode, the second electrode being on the organic light-emitting functional layer; The organic light-emitting functional layer comprises the triazine compound according to any one of claims 1 to 4.

8. The organic electroluminescent device according to claim 7, characterized in that: At least one of the organic light-emitting functional layers is an electron transport layer or a hole blocking layer, and the electron transport layer or the hole blocking layer comprises the triazine compound according to any one of claims 1 to 4.

9. Use of the organic electroluminescent device according to claim 7 in a display or lighting device.

10. A display or lighting device, characterized in that: The device comprises the organic electroluminescent device as claimed in claim 7.

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