An organic compound and an organic photoelectric element containing the same and its application

Abstract

The present invention provides an organic compound and an organic optoelectronic device containing the compound, and its applications, particularly an organic electroluminescent diode (OLED). The structure of the organic compound is represented by Formula (I) or (II). Detailed information about the organic compound and the organic optoelectronic device can be understood from the detailed description provided herein. The organic compound provided by the present invention can produce high-efficiency, low-operating-voltage OLED devices, demonstrating the potential application of such organic compounds in OLEDs and promising commercial application prospects.

Description

Technical Field

[0001] The present invention belongs to the field of organic photoelectric technology, and in particular relates to an organic compound and an organic photoelectric element containing the compound. Background Art

[0002] Among the related technologies, organic optoelectronic devices, especially organic electroluminescent devices (OLEDs), organic field-effect transistors (OFETs), and organic solar cells (OPVs), have attracted research from many scientists and industry circles. Among them, OLED or diodes, as a new generation of flat panel display technology, have gradually entered people's field of vision. Its broad application prospects and rapid technological progress in recent years have made OLED one of the hottest research areas in the field of flat panel information display and scientific research product development. The development of OLED technology in the display and lighting fields has always been constrained by the efficiency and lifespan of blue light OLEDs. High-efficiency blue light OLEDs can significantly improve display realism and reduce power consumption of display and lighting devices. In particular, the main reasons for the low luminous efficiency of blue light OLED devices are twofold: first, the low luminous efficiency of the core blue light guest material; second, the low energy transfer efficiency between the blue light host material and the guest material, mainly due to the low utilization rate of triplet excitons. Summary of the Invention

[0003] In order to solve the problems of low current efficiency and high operating voltage of OLED elements existing in existing OLED technology, the purpose of the present invention is to provide an organic compound and an organic optoelectronic element containing the compound, and to provide an organic compound with high luminous efficiency from the perspective of new material design; from the perspective of organic optoelectronic elements, the element structure with good charge transfer balance and high triplet exciton energy utilization in organic optoelectronic devices is significantly improved, so that the organic compound provided by the present invention and the organic optoelectronic element containing the compound, especially OLED, can have higher current efficiency and lower operating voltage, thereby significantly improving the overall performance of OLED.

[0004] The present invention is achieved through the following technical solutions:

[0005] The present invention provides an organic compound, which is represented by structural formulas (I) and (II).

[0006]

[0007] Structural formula (I), (II)

[0008] Wherein, in the structural formulas (I) and (II), R1 to R6 are the same or different and are selected from one of hydrogen, deuterium, F, CN, or a group of 1 to 60 carbon atoms, the group including alkyl, substituted or unsubstituted arylalkyl, alkoxy, substituted or unsubstituted aryloxy, alkylsilyl, alkoxy, alkylsiloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted heteroarylamino and combinations thereof; Ar1 ​​to Ar3 are the same or different and are selected from a group of 1 to 60 carbon atoms, the group including alkyl, Substituted or unsubstituted arylalkyl, alkoxy, substituted or unsubstituted aryloxy, alkylsilyl, alkoxy, alkylsiloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted heteroarylamino, and combinations thereof; the above-mentioned heteroaryl refers to a group containing at least one heteroatom selected from B, N, O, S, P(=O), Si, and P; any position of Ar1 to Ar3 may be fully or partially deuterated, fully or partially fluorinated; adjacent R1 to R5 and Ar2 to Ar3 may form a cyclic structure.

[0009] In the structural formulas (I) and (II) to be protected by the present invention, Ar1 to Ar3 are independently selected from groups having 1 to 60 carbon atoms, including alkyl, substituted or unsubstituted arylalkyl, alkoxy, substituted or unsubstituted aryloxy, alkylsilyl, alkoxy, alkylsiloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted heteroarylamino, and combinations thereof; any position of Ar1 to Ar3 may be fully or partially deuterated, fully or partially fluorinated; wherein, the substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl are independently selected from one or more of the following representative structures, but are not limited thereto:

[0010]

[0011]

[0012] wherein X is identical or different and represents BR, CRR, NR, O, S, or SiRR, wherein R is identical to R1 to R6 above, and may be fully or partially deuterated, fully or partially fluorinated; and n is 0, 1, 2, 3, or 4. In the organic compound structural formulas (I) and (II) of the present invention, Ar1 to Ar3 are independently selected from one or more of the following representative structures, but are not limited thereto:

[0013]

[0014]

[0015] *Indicates the position connected to the adjacent atom.

[0016] In the organic compound structural formulas (I) and (II) of the present invention, when R, R1 to R6 are identically or differently selected from one of hydrogen, deuterium, F, and CN, or selected from a group of 1 to 60 carbon atoms, they are particularly preferably selected from the following structures, but this does not mean that the selection of groups in the organic compound of the present invention is limited to these structures:

[0017]

[0018]

[0019] *Indicates the position connected to the adjacent atom.

[0020] The following representative structural formula represents one of the compounds described in structural formula (I), but is not limited thereto:

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030] The following representative structural formula represents one of the compounds described in structural formula (II), but is not limited thereto:

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] The present invention also provides a preparation comprising the organic compound of the present invention and at least one solvent or organic compound. The organic solvent or organic compound used is not particularly limited and may include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, hexyl chloride, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran and tetrahydropyran, ester solvents such as alkyl benzoates, or organic compounds.

[0040] The present invention also provides an organic photoelectric element, comprising a substrate, an anode layer located on the substrate, a functional layer located on the anode layer, and a cathode layer located on the functional layer.

[0041] In the organic optoelectronic device of the present invention, the functional layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer or an active layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof; the functional layer is composed of a mixture of the organic compound of the present invention and one or more organic compounds. The functional layer may further contain other organic compounds, metals, or metal compounds as dopants.

[0042] The organic photoelectric element described in the present invention is any one of an organic photovoltaic device, an organic light-emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-paper), an organic photoreceptor (OPC), an organic thin film transistor (OTFT) and an organic memory device (Organic Memory Element), a lighting and a display device.

[0043] In the present invention, the organic photoelectric element can be prepared by depositing metal or conductive oxides and their alloys on a substrate using methods such as sputtering, electron beam evaporation, and vacuum evaporation to form an anode; depositing a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, and an electron transport layer on the surface of the prepared anode in sequence, and then depositing a cathode. In addition to the above methods, an organic photoelectric element is prepared by depositing a cathode, an organic layer, and an anode on a substrate in sequence. The organic layer can also include a multilayer structure such as a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, and an electron transport layer. In the present invention, the organic layer is prepared using a polymer material according to solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing, or thermal-imaging, etc.) instead of the evaporation method, which can reduce the number of device layers.

[0044] The OLED elements made from the materials used in the present invention can be classified as top emission, low emission or double-sided emission.

[0045] The present invention also claims protection for display devices containing such OLED elements, in particular display devices based on AMOLED or PMOLED, including display screens for mobile phones, cameras, tablets, computers, televisions, projections, micro displays, e-books, etc., used to construct pixel units of display devices.

[0046] The present invention also claims protection for lighting devices or backlight sources containing organic electroluminescent elements, including OLED lamps, automobile taillights, LEDs, LCD element backlights, etc.

[0047] Beneficial effects of the present invention:

[0048] The present invention relates to a novel organic compound for use in organic optoelectronic devices, particularly organic electroluminescent diodes (OLEDs). Using the organic compound of the present invention and a corresponding host material as the light-emitting layer of an OLED device, the energy transfer between the host and the guest is highly efficient. Specifically, the organic electroluminescent device fabricated using the composition of the present invention as the light-emitting layer significantly improves its current efficiency while simultaneously reducing its operating voltage, significantly enhancing the overall performance of the OLED. The compound has promising commercial applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 Schematic diagram of the structure of the organic light-emitting element of the present invention. DETAILED DESCRIPTION

[0050] In order to help those skilled in the art better understand the present invention, the following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. 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 ordinary technicians in this field without creative work are within the scope of protection of this application.

[0051] Synthesis of compounds:

[0052] According to the technical basis of this field, the compounds involved in the present invention can be synthesized through the following reaction pathway:

[0053]

[0054] A halogen-containing substituted aminobiphenyl is used as a raw material, which is reacted with Ar1BCl2 in a solvent in a one-step method to obtain a halogen-containing substituted key intermediate, and then subjected to CC and CN coupling reactions to obtain the target compounds described in structural formulas (I) and (II) of the present invention.

[0055]

Synthesis of halogen-containing intermediate compounds

[0056] Under nitrogen protection, a halogen-containing substituted aminobiphenyl (10 mmol) was dissolved in o-dichlorobenzene (50 ml) and added dropwise to a solution of Ar1BCl2 (21 mmol) and o-dichlorobenzene (80 ml) at -40 to 5 degrees Celsius. After the addition was completed within 1 hour, the mixture was heated to room temperature and reacted for 10-12 hours. The temperature was then raised to reflux for 12-24 hours. After the reaction was completed, the mixture was cooled to room temperature and poured into ice water (200 ml) and extracted with dichloromethane. After all the above dichloromethane solutions were combined, the mixture was washed twice with 10% saturated sodium bicarbonate solution (80 ml), dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was washed with cold petroleum ether and passed through a silica gel column with petroleum ether / dichloromethane to obtain a halogen-containing intermediate compound. The yield results of LCMS detection are as follows:

[0057]

[0058] (2) Coupling reaction with RB(OH)2. Under nitrogen protection, the intermediate (10 mmol) and RB(OH)2 (11-33 mmol) were completely dissolved in tetrahydrofuran (120 ml) in a round-bottom flask. A 2M sodium carbonate aqueous solution (60 ml) was added, followed by tetrakis-(triphenylphosphine)palladium (0.2 g). The mixture was heated and stirred for 12 hours. After cooling to room temperature, the aqueous layer was removed. Dichloromethane (100 ml) was added, and the mixture was washed twice with 30 ml of saturated brine. The dichloromethane layer was dried over anhydrous magnesium sulfate, and the dichloromethane was removed by rotary evaporation. The crude product was passed through a silica gel column with petroleum ether / dichloromethane to obtain the target product.

[0059] (3) Coupling reaction with RR'NH. Under nitrogen atmosphere, the intermediate (10 mmol) and 1.1-3.3 equivalents of RR'NH were completely dissolved in xylene (80 ml) in a round-bottom flask. Then, sodium tert-butoxide (5-15 g) and bis(tri-tert-butylphosphine)palladium (0.1-0.3 g) were added. The mixture was heated under reflux for 6-18 hours. After cooling to room temperature, the salt was filtered off, the solvent was concentrated in vacuo, and the product was purified and separated on a silica gel column using petroleum ether: dichloromethane (20:1-2:1) as the eluent to obtain the target product.

[0060] The target product obtained in (2) or (3) is subjected to LCMS to determine its molecular structure, and is finally purified by high vacuum sublimation for use in the preparation of organic photoelectric devices.

[0061]

[0062] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific light emitting device embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0063] In a preferred embodiment of the present invention, the OLED device of the present invention comprises a hole transport layer. The hole transport material may be preferably selected from known or unknown materials, and is particularly preferably selected from the following structures, but this does not mean that the present invention is limited to the following structures:

[0064]

[0065] In a preferred embodiment of the present invention, the hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants. The preferred p-type dopant of the present invention has the following structure, but does not mean that the present invention is limited to the following structure:

[0066]

[0067] In the present invention, the compound represented by formula (1) or (2) is used as a hole transport material in a hole transport layer, a hole injection layer or an exciton blocking layer. The compound represented by formula (1) or (2) can be used alone, or the compound represented by formula (1) or (2) can be formed together with one or more of the above-mentioned p-type dopants.

[0068] In a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of compounds ET-1 to ET-13, but this does not mean that the present invention is limited to the following structures:

[0069]

[0070] The electron transport layer may be formed of an organic material and one or more n-type dopants (eg, LiQ).

[0071] The present invention also provides a preparation comprising the composition and a solvent. The solvent used is not particularly limited and can include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, and the like; halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, hexyl chloride, bromohexane, chlorocyclohexane, bromocyclohexane; halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; ether solvents such as tetrahydrofuran and tetrahydropyran; and ester solvents such as alkyl benzoates. The preparation can be directly used to prepare a photovoltaic device.

[0072] like Figure 1 As shown, the organic optoelectronic device includes a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer or active layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, and a cathode 110.

[0073] Fabrication of OLED devices:

[0074] The specific structure of the bottom-emitting OLED device is as follows: on glass containing ITO, the HIL is HT-1:P-3 (97:3v / v%) with a thickness of 10 nanometers; the HTL is HT-1 with a thickness of 90 nanometers; the EBL is HT-10 with a thickness of 10 nanometers, the EML is BH-1:organic compound (97:3v / v%) with a thickness of 35 nanometers, the ETL is ET-2:LiQ (50:50v / v%) with a thickness of 35 nanometers, and then the cathode Al is evaporated to 40 nanometers.

[0075] In order to better illustrate the actual gain effect of the present invention, a commonly used guest compound BD-1 was doped into the host material BH-1 for comparison to prepare a corresponding comparative OLED device.

[0076]

[0077] According to the above device embodiments, the external quantum efficiency (EQE), voltage, lifespan and other characteristics of the OLED device are shown in Table 1 below.

[0078] Table 1

[0079]

[0080] The above device results show that the comparative device 1 uses the guest materials BD-1 and BH-1 to form the light-emitting layer of the device. In the preferred device, the organic compound of the present invention replaces BD-1, the efficiency of the device is improved, and the driving voltage remains the same or decreases. The guest material BD-1 has a similar structure to the organic compounds TM-1131 and TM-2847 of the present invention. After being used as the guest material and forming the light-emitting layer with BH-1, the current efficiency of device examples 8 and 11 is increased to 109% to 111% compared with the comparative device 1, and the driving voltage is reduced. There is a significant improvement in the overall performance of the light-emitting device. The present invention provides a new BN-type organic compound to realize OLED devices with high current efficiency and low driving voltage, and the overall performance of the light-emitting device is improved significantly.

[0081] While the embodiments of the present invention have been described in detail above, those skilled in the art will readily appreciate other embodiments of the present invention after considering the specification and practicing the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the present application that follow the general principles of the present application and include common knowledge or customary techniques in the art not disclosed herein. The description and examples are to be considered merely as exemplary, and the true scope and spirit of the present application are indicated by the following claims.

[0082] It should be understood that the present application is not limited to the precise structure described and illustrated above, and various modifications and changes can be made without departing from the scope of the present application. The scope of the present application is limited only by the appended claims. The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. An organic compound, wherein the organic compound is represented by structural formula (I) and (II): ； In structural formulas (I) and (II), R1 to R6 are independently selected from hydrogen, or one or more of the following structures: ； Ar1 to Ar3 are independently selected from one or more of the following structures: ; in, *Indicates the position connected to the adjacent atom.

2. An organic compound, characterized in that The organic compound is represented by the following compound: 。 3. A preparation, characterized in that The method comprises the organic compound according to claim 1 or 2 and at least one solvent, wherein the solvent is selected from toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, hexyl chloride, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrahydrofuran, tetrahydropyran or alkyl benzoate.

4. An organic photoelectric element, characterized in that: include: a first electrode; a second electrode facing the first electrode; an organic functional layer, sandwiched between the first electrode and the second electrode; Wherein, at least one layer of the organic functional layer comprises the organic compound according to claim 1 or 2.

5. The organic photoelectric element according to claim 4, characterized in that The organic functional layer includes one consisting of a light emitting layer, a hole transport layer, a hole injection layer, an electron injection layer, a hole blocking layer and a combination thereof.

6. The organic photoelectric element according to claim 5, characterized in that The organic functional layer further contains other organic compounds as dopants.

7. The organic photoelectric element according to claim 5, characterized in that The organic photoelectric element is an electroluminescent diode, and its light-emitting layer comprises the organic compound according to claim 1 or 2. 8 . A display device or a lighting device, comprising the organic photoelectric element according to claim 4 .

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