TWI617547B - Organic material and organic electroluminescence device using the same - Google Patents

Abstract

The present invention discloses an organic material including a derivative of indenotriphenylene. The organic material can be applied with a hole blocking layer, an electron transporting layer, and / or a phosphorescent light-emitting body of an organic EL device. The device thus prepared can effectively reduce a driving voltage, reduce power consumption, and increase efficiency. The invention further discloses a method for preparing an indenotriphenylene derivative and an organic electroluminescent device including the foregoing organic material.

Description

Organic material and organic electroluminescent device using the same

The present invention generally relates to an organic material containing an indenotriphenylene derivative and an organic electroluminescent (hereinafter referred to as an organic EL) element using the organic material. More specifically, the present invention relates to an organic material having a compound of formula (I). Using this material as a hole blocking layer (HBL), an electron transport layer (ETL), and / or a phosphorescent host can effectively reduce driving voltage and power. Consumption and increase efficiency.

Organic electroluminescence (organic EL) is a type of light-emitting diode (LED) in which the light-emitting layer is a film made of an organic compound that emits light at a corresponding current. The light emitting layer of the organic compound is sandwiched between two electrodes. Organic EL is used in flat panel displays due to its high lighting, low weight, ultra-thin profile, self-illuminating without backlight, low power consumption, wide viewing angle, high contrast, simple manufacturing method and fast response time.

The first observation of the electrical excitation of organic materials was performed by Andre Bernanose and colleagues at the Nancy Université in France in the early 1950s. New York University's Martin Pope and his colleagues observed direct current (DC) electrical excitation light in a vacuum for the first time in 1963 on a single pure crystal doped with tetracene anthracene.

The first diode element was published in 1987 by Ching W. Tang and Steven Van Slyke of Eastman Kodak. The device uses a two-layer structure with a hole transport layer and an electron transport layer separately installed, which reduces the operating voltage and improves efficiency, leading the research and production of organic EL in the current era.

Typically, the organic EL system is composed of an organic material layer located between two electrodes, which includes a hole transporting layer (HTL), a light emitting layer (EML), and an electron transporting layer. , ETL). The basic mechanism of organic EL involves carrier injection, carrier transport, recombination, and exciton formation to emit light. When an external voltage is applied to the organic light-emitting element, electrons and holes are injected from the cathode and anode, respectively. Electrons are injected from the cathode into the lowest unoccupied molecular orbital (LUMO), and holes are injected from the anode To the highest occupied molecular orbital (HOMO). When electrons and holes recombine in the light-emitting layer, excitons are formed and then emit light. When a light-emitting molecule absorbs energy to reach an excited state, the exciton can be in a singlet state or a triplet state depending on the spin combination of the electron and the hole. 75% of the excitons are formed by the recombination of electrons and holes to reach the triplet excited state. Attenuation from the triplet state is self forbidden. Therefore, the fluorescent light-excitation light element has an internal quantum efficiency of only 25%. Compared to fluorescent light-emitting devices, phosphorescent organic EL devices use spin-orbit interaction to promote the intersystem crossing between singlet and triplet states. And triplet states, and the internal quantum efficiency of the electrically excited light element has increased from 25% to 100%. Spin-orbit interactions can be accomplished by heavy atoms such as iridium, rhodium, platinum, palladium, etc., and can be obtained from organometallic complexes Phosphorescent transition was observed in the excited metal to ligand charge transfer (MLCT).

In recent years, Professor Adachi and his colleagues have developed a new type of fluorescent organic EL device that combines thermally activated delayed fluorescence (TADF) mechanism. It uses reverse intersystem crossing , RISC) mechanism, a promising way to convert spin-blocked triplet excitons to singlet energy levels to obtain high efficiency of exciton formation.

Both triplet and singlet exciton can be utilized by phosphorescent organic EL. Compared with singlet excitons, triplet excitons have a longer half-life and diffusion length. Phosphorescent organic ELs generally require an additional hole blocking layer (HBL) between the light-emitting layer and the electron transport layer. Or an electron blocking layer (EBL) between the light emitting layer and the hole transport layer is required. The purpose of using a hole blocking layer or an electron blocking layer is to limit the recombination between the injected holes and electrons, and to relax the excitons generated in the light emitting layer, thereby improving the efficiency of the device. In order to satisfy these effects, hole blocking materials or electron blocking materials must have HOMO and LUMO energy levels suitable for blocking the transmission of holes or electrons from the light emitting layer to the electron transport layer or to the hole transport layer.

There is a continuing need for organic EL materials that can effectively transport electrons or holes, can block holes, and have good thermal stability and high luminous efficiency. For the reasons described above, an object of the present invention is to solve these problems of the prior art and provide an organic EL element that is quite excellent in terms of thermal stability, high brightness, and long half-life time. The present invention discloses a novel organic material having an indenotriphenylene derivative of formula (I), which is used as a hole blocking layer (HBL), an electron transport layer (ETL), and / or a phosphorescent host, and has good charge carrier movement. Performance and excellent operation durability, can reduce the driving voltage and power consumption of organic EL elements, improve efficiency and half-life time.

According to the present invention, there is provided a use for a hole blocking material (hereinafter referred to as HBM), an electron transport material (ETM), and / or a phosphorescent host and an organic EL element thereof. This organic material can overcome the lack of existing materials, such as low efficiency and high power consumption.

An object of the present invention is to provide an organic material that can be used as a hole blocking material (HBM) and a hole electron transport material (HBETM) of an organic EL element, which can effectively limit exciton transfer to an electron transport layer.

An object of the present invention is to provide an organic material that can be used as an electron transport material (ETM) of an organic EL element.

An object of the present invention is to provide a phosphorescent host material that can be used as a light emitting layer of an organic EL element.

Another object of the present invention is to apply the aforementioned organic material to an organic EL device, and can effectively reduce the driving voltage, reduce power consumption, and increase efficiency.

The invention has the economic advantages of industrial practice. According to the present invention, an organic material that can be used in an organic EL device is disclosed. The aforementioned organic material is represented by the following formula (I): Formula (I) wherein Ring A represents a phenyl group and a fused ring hydrocarbon unit having two to four ring groups, and L represents a single bond, a substituted or unsubstituted divalent subunit having 6 to 30 ring carbon atoms. An aryl group (divalent arylene group) or a substituted or unsubstituted divalent heteroarylene group having 6 to 30 ring carbon atoms, and R ₁ to R ₃ independently represent selected from the group consisting of a hydrogen atom , Substituted or unsubstituted alkyl groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted groups having 6 to 30 carbon atoms Substituted aralkyl and substituted or unsubstituted heteroaryl having 6 to 30 carbon atoms, Y ₁ to Y ₅ each independently represent a nitrogen atom or CR ₅ , R ₅ independently represents a hydrogen atom, and has 6 A substituted or unsubstituted phenylene group to 30 carbon atoms or a bond to B, B is represented by the following formula (II): Formula (II) wherein q represents an integer of 0 to 3, p represents an integer of 0 to 7, X represents O, S, NR ₆ , and R ₆ independently represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted Or an unsubstituted carbazolyl group and a bond to formula (I), R ₄ has the same definition as R ₁ .

The present invention is to explore an organic material and an organic EL element using the organic material. A detailed description of production, structure, and elements will be provided below to fully understand the present invention. Obviously, the application of the present invention is not limited to the specific details familiar to those skilled in the art. On the other hand, known common elements and procedures are not described in detail in the present invention, and should not unnecessarily limit the present invention. Some preferred embodiments of the present invention will now be described in more detail below. However, it should be recognized that the present invention can be widely practiced in a variety of other embodiments besides the explicitly described embodiments, that is, the present invention can be widely applied to other embodiments and except as specified in the scope of the attached application patent In addition, the scope of the present invention is not explicitly limited.

In a first embodiment of the present invention, a hole blocking layer (hereinafter referred to as HBM), an electron transporting layer (hereinafter referred to as ETM), and / or a phosphorescent host that can be used in an organic EL element are disclosed. The aforementioned organic material is represented by the following formula (I): Formula (I) wherein Ring A represents a phenyl group and a fused ring hydrocarbon unit having two to four ring groups, and L represents a single bond, a substituted or unsubstituted divalent subunit having 6 to 30 ring carbon atoms. An aryl group (divalent arylene group) or a substituted or unsubstituted divalent heteroarylene group having 6 to 30 ring carbon atoms, and R ₁ to R ₃ independently represent selected from the group consisting of a hydrogen atom , Substituted or unsubstituted alkyl groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted groups having 6 to 30 carbon atoms Substituted aralkyl and substituted or unsubstituted heteroaryl having 6 to 30 carbon atoms, Y ₁ to Y ₅ each independently represent a nitrogen atom or CR ₅ , R ₅ independently represents a hydrogen atom, and has 6 A substituted or unsubstituted phenylene group to 30 carbon atoms or a bond to B, B is represented by the following formula (II): Formula (II) wherein q represents an integer of 0 to 3, p represents an integer of 0 to 7, X represents O, S, NR ₆ , and R ₆ independently represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted Or an unsubstituted carbazolyl group and a bond to formula (I), R ₄ has the same definition as R ₁ .

According to the above formula (I), L is represented by the following formula:

According to the above formula (I), wherein the ring A represents a phenyl group and a fused ring hydrocarbon unit having two to four ring groups, including naphthyl, anthracenyl, phenanthryl, fluorenyl, chrysyl, and triphenylene.

In this embodiment, some organic materials are expressed according to formula (I) as follows: .

The detailed preparation of the organic material according to the present invention can be illustrated by the exemplary embodiments, but is not limited to the exemplary embodiments. Examples 1 to 14 show the preparation of some examples of organic materials in the present invention. Examples 15 to 16 show the I-V-B, half-life time of organic EL element manufacturing and organic EL element test reports.

Example 1: Synthesis of Compound EX5

Synthesis of 2-bromo-5-nitrobiphenyl

2.6 g (12.14 mmol) of 2-phenyl-4-nitroaniline was added to a mixture of 0.92 g (13.35 mmol) of sodium nitrite, 8 ml of sulfuric acid, and 9 ml of acetic acid at 0-5 ° C, and at 0-5 ° C Stir for 2 hours. Water was added to this mixture and stirred at room temperature for 1 hour. 4.3 g (19.42 mmol) of copper (II) bromide was dissolved in 9.3 ml of a 2M HCl solution and added and stirred at room temperature for 20 minutes, followed by heating for 1 hour to 60 ° C. After the reaction was completed, the organic layer was extracted with ether and water, washed with brine, dried over magnesium sulfate and evaporated to dryness. The crude product was purified by silica gel-filled column chromatography to obtain the product (1.5 g, 5.39 mmol, 45.5%).

Synthesis of 9,9-dimethyl-2- (5-nitrobiphenyl-2-yl) -9H-fluorene

40 g (14.38 mmol) of 2-bromo-5-nitrobiphenyl, 27.7 g (15.82 mmol) of 9,9-dimethyl-9H-fluoren-2-ylboronic acid, 1.8 g (0.16 mmol) of tetrakis (triphenyl) A mixture of phosphino) palladium, 119 ml of 2M sodium carbonate, 150 ml of ethanol, and 450 ml of toluene was degassed and placed under nitrogen, followed by heating at 100 ° C overnight. After the reaction was completed, the mixture was cooled at room temperature. The solution was extracted with dichloromethane and water. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure. The residue was purified by silica-filled column chromatography to obtain 43.1 g of the product (110.1 mmol, 9.6%). 1H NMR (CDCl ₃ , 400MHz): Chemical shift (ppm) 7.93 (s, 1H), 7.71 (d, 1H), 7.50 (d, 1H), 7.38 ~ 7.21 (m, 6H), 7.16 ~ 6.92 (m, 4H), 6.83 ~ 6.65 (m, 2H), 1.15 (s, 6H).

Synthesis of 6- (9,9-dimethyl-9H-fluoren-2-yl) biphenyl-3-amine

A mixture of 10.4 g (26.56 mmol) of 9,9-dimethyl-2- (5-nitrobiphenyl-2-yl) -9H-fluorene, 8.5 g (159.36 mmol) of iron powder and 10 ml of concentrated hydrochloric acid The mixture was refluxed in an aqueous alcohol solution (100 mL of alcohol and 30 mL of water) at 85 ° C for 2 hours. The reaction mixture was filtered and the filtrate was extracted with ethyl acetate and water. The organic layer was dried with anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The formed solid was washed with hexane to obtain 8.2 g of product (22.68 mmol, 85%). 1H NMR (CDCl ₃ , 400MHz): Chemical shift (ppm) 7.71 (d, 1H), 7.64 (d, 1H), 7.42 (d, 1H), 7.29 ~ 7.12 (m, 7H), 7.06 (d, 2H), 6.89 (s, 1H), 6.80 (d, 1H), 6.78 (s, 1H), 4.47 (s, 2H), 1.12 (s, 6H).

Synthesis of 2- (5-bromobiphenyl-2-yl) -9,9-dimethyl-9H-fluorene

0.6g (2.76mmol) of anhydrous copper (II) bromide, anhydrous acetonitrile (46mL), and 1g (2.76mmol) of the corresponding 6- (9,9-dimethyl-9H-fluoren-2-yl) -diamine Phenyl-3-amine was slowly added to the reflux mixture of 0.34 g (3.32 mmol) of tert-butyl nitrite over 1 hour, resulting in a reaction with vigorous foaming and evolution of nitrogen. After the reaction was completed, the mixture was cooled to room temperature and poured into an aqueous hydrochloric acid solution. The precipitated crude product was purified by silica-filled column chromatography to obtain 0.3 g of the product (0.70 mmol, 25%). 1H NMR (CDCl ₃ , 400MHz): Chemical shift (ppm) 7.81 (d, 1H), 7.68 ~ 7.66 (m, 1H), 7.63 ~ 7.61 (m, 1H), 7.37 ~ 7.35 (m, 1H), 7.32 ~ 7.24 (m, 4H), 7.22 ~ 7.16 (m, 4H), 7.12 ~ 7.09 (m, 2H), 6.93 (d, 1H), 1.20 (s, 6H).

Synthesis of 6-bromo-10,10-dimethyl-10H-indeno [2,1-b] triphenylene

In a 100 ml three-necked flask filled with deaeration and filled with nitrogen, 2.9 g (0.68 mmol) of 2- (5-bromobiphenyl-2-yl) -9,9-dimethyl-9H-fluorene was dissolved in Anhydrous dichloromethane (180 ml), 5.5 g (3.40 mmol) of iron (III) chloride, and the mixture was stirred for one hour. The reaction was quenched with methanol and water, and the organic layer was separated and the solvent was removed. The residue was purified by silica gel-filled column chromatography to obtain a white solid (1.7g, 0.81mmol, 58.6%). 1H NMR (CDCl ₃ , 400MHz): Chemical shift (ppm) 9.01 (s, 1H), 8.94 (d, 2H), 8.78 (s, 1H), 8.58 (s, 1H), 8.49 (s, 1H), 7.98 (d, 1H), 7.85 ~ 7.78 (m, 2H), 7.63 ~ 7.43 (m, 4H ), 1.69 (s, 6H).

Synthesis of 2- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) -4,4,5,5-tetramethyl-1,3,2-di Oxetane

A mixture of 3 g (7 mmol) of 6-bromo-10,10-dimethyl-10H-indeno [2,1-b] triphenylene, 2.16 g (8.4 mmol) of 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bis (1,3,2-dioxorane), 0.16 g (0.14 mmol) tetrakis (triphenylphosphino) palladium 50 ml of 1,4-dioxane was degassed and placed under nitrogen, followed by heating at 100 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was purified by column chromatography filled with silica gel to obtain a white solid product (2.27 g, 4.8 mmol, 69%).

Synthesis of 2- (4- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -4,6-diphenyl-1,3,5 -Triazine (EX5)

3g (6.38mmol) of 2- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) -4,4,5,5-tetramethyl-1, 3,2-dioxorane, 1.90 g (4.90 mmol) 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine, 0.05 g (0.05 mmol ) A mixture of tetrakis (triphenylphosphino) palladium, 9.8 ml of 2M sodium carbonate, 15 ml of ethanol, and 45 ml of toluene was degassed and placed under nitrogen, and heated at 100 ° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer was extracted with dichloromethane and water, dried over anhydrous magnesium sulfate, and the solvent was removed. The residue was purified by silica gel-filled column chromatography to obtain a pale yellow product (1.75 g, 2.67 mmol, 55%). 1H NMR (CDCl ₃ , 400MHz): Chemical shift (ppm) 9.03 (s, 1H), 8.97 ~ 8.77 (m, 3H), 8.58 (s, 1H), 8.49 ~ 8.31 (m, 7H), 7.98 (d, 1H), 7.85 ~ 7.78 (m, 2H), 7.63 ~ 7.43 (m, 12H), 1.69 (s, 6H). MS (m / z, FAB ⁺ : 651.5.

Example 2: Synthesis of Compound EX9

Synthesis of 2- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) -4,6-diphenyl-1,3,5-triazine

In addition to replacing 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine with 2-chloro-4,6-diphenyl-1,3,5-triazine Except for the rest, the same method as in Example 1 was used to obtain the product 2- (10,10-dimethyl-10H-indeno [2,1-b] triphenyl-6-yl) -4,6-di Phenyl-1,3,5-triazine (1.26 g, yield = 45%). MS (m / z, FAB ⁺ ): 575.6.

Example 3: Synthesis of Compound EX10

Synthesis of 2- (3- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -4,6-diphenylpyrimidine

Replace 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine with 2- (3-bromophenyl) -4,6-diphenylpyrimidine, and the rest Using the same method as in Example 1, the product 2- (3- (10,10-dimethyl-10H-indeno [2,1-b] triphenyl-6-yl) phenyl) -4,6 was obtained. -Diphenylpyrimidine (3.08 g, yield = 63%). MS (m / z, FAB ⁺ ): 650.8.

Example 4: Synthesis of Compound EX15

Synthesis of 2- (3- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -4,6-bis ([1,1 ': 3 ', 1''-terphenyl]-5'-yl) -1,3,5-triazine

Replace 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine with 2- (4-bromophenyl) -bromophenyl-4,6-bis ([1, 1 ': 3', 1 ''-terphenyl] -5'-yl) -1,3,5-triazine, and the rest were used in the same manner as in Example 1 to obtain product 2- (3- (10,10 -Dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -4,6-bis ([1,1 ': 3', 1 ''-terphenyl]- 5'-yl) -1,3,5-triazine (1.96 g, yield = 42%). MS (m / z, FAB ⁺ ): 957.2.

Example 5: Synthesis of Compound EX33

Synthesis of 9,9 '-(6- (4- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -1,3,5-tris Azine-2,4-diyl) bis (9H-carbazole)

2 g (4.25 mmol) of 2- (10,10-dimethyl-10H-indeno [2,1-b] triphenyl-6-yl) -4,4,5,5-tetramethyl-1, 3,2-dioxorane, 1.85 g (3.26 mmol) 9,9 '-(6- (4-bromophenyl) -1,3,5-triazine-2,4-diyl) Bis (9H-carbazole), 0.04g (0.03mmol) tetrakis (triphenylphosphino) palladium, 3.25ml 2M sodium carbonate, 10ml ethanol and 30ml toluene were degassed and placed under nitrogen, then at 100 ° C Heat for 12 hours. After the reaction was completed, the mixture was cooled to room temperature. The organic layer was extracted with dichloromethane and water, dried over anhydrous magnesium sulfate, and the solvent was removed. The residue was purified by silica gel-filled column chromatography to obtain a pale yellow solid product (1.24 g, 1.50 mmol, 46%). 1H NMR (CDCl ₃ , 400MHz): Chemical shift (ppm) 9.08 (s, 1H), 8.97 ~ 8.77 (m, 3H), 8.53 ~ 8.29 (m, 8H), 7.92 ~ 7.78 (m, 7H), 7.63 ~ 7.43 (m, 14H), 1.69 (s, 6H). MS (m / z, FAB ⁺ ): 831.0.

2 g (4.25 mmol) of 2- (10,10-dimethyl-10H-indeno [2,1-b] triphenyl-6-yl) -4,4,5,5-tetramethyl-1, 3,2-dioxorane, 1.85 g (3.26 mmol) 9,9 '-(6- (4-bromophenyl) -1,3,5-triazine-2,4-diyl) Bis (9H-carbazole), 0.04g (0.03mmol) tetrakis (triphenylphosphino) palladium, 3.25ml 2M sodium carbonate, 10ml ethanol and 30ml toluene were degassed and placed under nitrogen, then at 100 ° C Heat for 12 hours. After the reaction was completed, the mixture was cooled to room temperature. The organic layer was extracted with dichloromethane and water, dried over anhydrous magnesium sulfate, and the solvent was removed. The residue was purified by silica-filled column chromatography to obtain a pale yellow product (1.24 g, 1.50 mmol, 46%). 1H NMR (CDCl ₃ , 400MHz): Chemical shift (ppm) 9.08 (s, 1H), 8.97 ~ 8.77 (m, 3H), 8.53 ~ 8.29 (m, 8H), 7.92 ~ 7.78 (m, 7H), 7.63 ~ 7.43 (m, 14H), 1.69 (s, 6H). MS (m / z, FAB ⁺ ): 831.0.

Example 6: Synthesis of Compound EX37

Synthesis of 9,9 '-(2- (3- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) pyrimidin-4,6-diyl ) Bis (9H-carbazole)

Replace 9,9 '-(6- (4-bromophenyl) -1,3,5-triazine-2,4-diyl) bis (9H-carbazole) with 9,9'-(2- (3-Bromophenyl) pyrimidine-4,6-diyl) bis (9H-carbazole), the rest are the same as the method of Example 5 to obtain the product 9,9 '-(2- (3- (10,10 -Dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) pyrimidin-4,6-diyl) bis (9H-carbazole) (1.18 g, yield = 44 %). MS (m / z, FAB ⁺ ): 829.8.

Example 7: Synthesis of Compound EX38

Synthesis of 9,9 '-(2- (3- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) pyrimidin-4,6-diyl ) Bis (9H-carbazole)

Replace 9,9 '-(6- (4-bromophenyl) -1,3,5-triazine-2,4-diyl) bis (9H-carbazole) with 9- (4- (4- Bromophenyl) -6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole, the rest are the same as the method of Example 5 to obtain the product 9- (4- (4- (10 , 10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -6-phenyl-1,3,5-triazin-2-yl) -9H- Carbazole (1.20 g, yield = 50%). MS (m / z, FAB ⁺ ): 741.5.

Example 8: Synthesis of Compound EX42

Synthesis of 9- (4- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -9H-carbazole

2 g (4.25 mmol) of 2- (10,10-dimethyl-10H-indeno [2,1-b] triphenyl-6-yl) -4,4,5,5-tetramethyl-1, 3,2-dioxorane, 1.05g (3.26mmol) 9- (4-bromophenyl) -9H-carbazole, 0.04g (0.03mmol) tetrakis (triphenylphosphino) palladium, 3.25ml A mixture of 2M sodium carbonate, 10 ml of ethanol, and 30 ml of toluene was degassed and placed under nitrogen, followed by heating at 100 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature. The organic layer was extracted with dichloromethane and water, dried over anhydrous magnesium sulfate, and the solvent was removed. The residue was purified by silica-filled column chromatography to obtain a pale yellow product (1.43 g, 2.45 mmol, 75%). 1H NMR (CDCl ₃ , 400MHz): Chemical shift (ppm) 9.01 (s, 1H), 8.82 (d, 2H), 8.77 (s, 1H), 8.55 (s, 1H), 8.49 (s, 1H), 7.98 (d, 1H), 7.85 ~ 7.75 (m, 6H), 7.63 ~ 7.33 (m, 12H), 1.69 (s, 6H). MS (m / z, FAB ⁺ ): 586.3.

Example 9: Synthesis of Compound EX44

Synthesis of 9,9 '-(5- (10,10-dimethyl-10H-indeno [2,1-b] Anylidene-6-yl) -1,3-phenylene) bis (9H-carbazole )

9- (4-bromophenyl) -9H-carbazole was replaced with 9,9 '-(5-bromo-1,3-phenylene) bis (9H-carbazole), and the rest were the same as in Example 8. The product 9,9 '-(5- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) -1,3-phenylene) bis (9H-carb Azole) (1.46 g, yield = 60%). MS (m / z, FAB ⁺ ): 751.4.

Example 10: Synthesis of Compound EX50

Synthesis of 9- (4- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -9'-phenyl-9H, 9'H-3 3'-biscarbazole

9- (4-bromophenyl) -9H-carbazole was replaced with 9- (4-bromophenyl) -9'-phenyl-9H, 9'H-3,3'-biscarbazole, and the rest were followed by The method of Example 8 was the same, and the product 9- (4- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -9'-phenyl- 9H, 9'H-3,3'-biscarbazole (1.28g, yield = 48%). MS (m / z, FAB ⁺ ): 827.9.

Example 11: Synthesis of Compound EX51

Synthesis of 3- (3- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -9-phenyl-9H-carbazole

9- (4-bromophenyl) -9H-carbazole was replaced with 3- (3-bromophenyl) -9-phenyl-9H-carbazole, the rest were the same as in Example 8 to obtain product 3- (3- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) -9-phenyl-9H-carbazole (1.28g, yield = 48%). MS (m / z, FAB ⁺ ): 662.7.

Example 12: Synthesis of compound EX55

Synthesis of 4- (3- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) phenyl) dibenzo [b, d] thiophene

2 g (4.25 mmol) of 2- (10,10-dimethyl-10H-indeno [2,1-b] triphenyl-6-yl) -4,4,5,5-tetramethyl-1, 3,2-dioxorane, 1.10 g (3.26 mmol) 4- (3-bromophenyl) diphenyl [b, d] thiophene, 0.04 g (0.03 mmol) tetrakis (triphenylphosphino) Palladium, 3.25 ml of 2M sodium carbonate, 10 ml of ethanol, and 30 ml of toluene were degassed and placed under nitrogen, followed by heating at 100 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature. The organic layer was extracted with dichloromethane and water, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was purified by silica gel-filled column chromatography to obtain a pale yellow product (1.62 g, 2.61 mmol, 80%). 1H NMR (CDCl ₃ , 400MHz): Chemical shift (ppm) 9.03 (s, 1H), 8.86 (d, 2H), 8.70 (s, 1H), 8.49 (s, 1H), 8.46 (s, 1H), 7.96 (d, 1H), 7.85 ~ 7.76 (m, 2H), 7.68 ~ 7.25 (m, 15H), 1.69 (s, 6H). MS (m / z, FAB ⁺ ): 603.5.

Example 13: Synthesis of Compound EX56

Synthesis of 2,2 '-(5- (10,10-dimethyl-10H-indeno [2,1-b] 0 triphenylene-6-yl) -1,3-phenylene) dibenzo [b , d) furan

Replace 4- (3-bromophenyl) dibenzo [b, d] thiophene with 2,2 '-(5-bromo-1,3-phenylene) dibenzo [b, d] furan, the rest are In the same manner as in Example 12, the product 2,2 '-(5- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) -1,3- Benzene) dibenzo [b, d] furan (1.30 g, yield = 53%). MS (m / z, FAB ⁺ ): 752.9.

Example 14: Synthesis of Compound EX57

Synthesis of 4- (3 '-(10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) biphenyl-3-yl) dibenzo [b, d] thiophene

Replace 4- (3-bromophenyl) dibenzo [b, d] thiophene with 4- (3'-bromobiphenyl-3-yl) dibenzo [b, d] thiophene, and the rest are all examples The method of 12 is the same, and the product 4- (3 '-(10,10-dimethyl-10H-indeno [2,1-b] triphenylene-6-yl) biphenyl-3-yl) dibenzo is obtained. [b, d] Thiophene (1.30 g, yield = 53%). MS (m / z, FAB ⁺ ): 679.5.

General method for producing organic EL elements

According to the present invention, an indium tin oxide (ITO) -coated glass (hereinafter referred to as an ITO substrate) is provided, having a resistance of 9 ohm / square to 12 ohm / square and a thickness of 120. nm to 160 nm and cleaned in an ultrasonic bath using multiple cleaning steps (eg detergents, deionized water). Prior to the vapor deposition of the organic layer, the cleaned ITO substrate was further treated with UV and ozone. All pre-treatment processes for ITO substrates are performed in a clean room (Class 100) environment.

In a high vacuum unit (10 -7 Torr) such as a resistively heated quartz boat, these organic layers are sequentially coated on an ITO substrate by vapor deposition. Precisely monitor or set the thickness of the corresponding layer and the vapor deposition rate (0.1 nm / sec to 0.3 nm / sec) with a quartz-crystal monitor. As mentioned above, individual layers may also consist of more than one compound, meaning a host material doped with a dopant material in general. This type of material can be achieved by co-vaporization from two or more sources

Dipyrazino [2,3-f: 2,3-] quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN) is used as a hole in organic EL elements Injection material, N, N-bis (naphthalene-1-yl) -N, N-bis (phenyl) -benzidine (NPB) Most commonly used as hole transport material, 10,10-dimethyl-12- (10- (naphthalene-2-yl) anthracene-9-yl) -10H-indeno [2,1-b] triphenylene (H1) is used as a blue light emitting host, and N1, N1, N6, N6-tetra- M-Tolylfluorene-1,6-diamine (D1) is used as a blue light guest, 2- (10,10-dimethyl-10H-indeno [2,1-b] triphenylene-13-yl) -4 , 6-Diphenylpyrimidine (HB1) is used as a hole blocking material (HBM) and 4,7-diphenyl-2,9-bis (4- (1-phenyl-1H-benzo [d] imidazole) -2-yl) phenyl) -1,10-phenanthroline (LT-N8001, refer to U.S. Patent No. 7,754,348) is used as an electron transport material (ETM) in organic EL elements to communicate with LiQ) co-deposition. Bis (2-methyl-8-quinoline) -4- (phenylphenol) aluminum (BAlq) is used as a hole blocking material (HBM) or as a phosphorescent host in a phosphorescent system. , 4-Diphenylpyridine) iridium (III) (D2) is used as a phosphorescent dopant. The above-mentioned prior art OLED materials that can be used to generate a standard organic EL element control group and the comparative materials in the present invention are shown in the following chemical structure:

A typical organic EL element is composed of a low-work-function metal material such as Al, Mg, Ca, Li, and K. The low-work-function metal material can assist electron injection from the cathode to the electron transport layer by thermal evaporation as a cathode. . In addition, in order to reduce the barrier of electron injection and improve the performance of the organic EL element, a thin-film electron injection layer is introduced between the cathode and the electron transport layer. Conventional materials for the electron injection layer are metal halides or metal oxides having a low work function, such as LiF, LiQ, MgO, or Li 2 O. On the other hand, after the organic EL element is manufactured, EL spectra and CIE coordination are measured by using a PR650 spectra scan spectrometer. In addition, Keithley 2400 programmable voltage-current source (Keithley 2400 programmable voltage-current source) to obtain current / voltage, luminescence / voltage, and yield / voltage characteristic data. The above equipment is operated at room temperature (about 25 ° C) and atmospheric pressure.

Example 15

Using a procedure similar to the general method described above, a blue fluorescent organic EL element with the following element structure (see Figure 1) was produced, and the element structure was: ITO / HAT-CN (20nm) / NPB (130nm) / doped 5% D1 H1 (30nm) / HBM (10nm) / ETM co-deposited with LiQ (ETM: LiQ ratio = 1: 1) (40nm) / LiQ (1nm) / Al (160nm). The IVB (at 1000 nits) and half-life time of the blue fluorescent organic EL device test report are shown in Table 1. The half-life time is defined as the time at which the initial brightness of 1000 cd / m ² is reduced to half.

Table 1

Example 16

Using a procedure similar to the general method described above, a phosphorescent organic EL element with the following element structure (see Figure 1) was generated, and the element structure was: ITO / HAT-CN (20nm) / NPB (130nm) / phosphorescent host (PHhost) + 15% D2 (30nm) / HBM (15nm) / EX5 co-deposited with LiQ (EX5: LiQ, ratio = 1: 1) (40nm) / LiQ (1nm) / Al (160nm). Table 2 shows the IVB (at 1000 nits) and half-life time of the phosphorescent organic EL device test report. The half-life time is defined as the time at which the initial brightness of 3000 cd / m ² is reduced to half.

Table 2

Please refer to Table 1 and Table 2. In the preferred embodiment of the above organic EL device test report, it is shown that the organic material of formula (I) of the present invention is applied to a hole blocking material, an electron transporting material, and / Or in phosphorescent host, compared with the prior art OLED material, the device can achieve better performance.

In summary, the present invention discloses a novel organic material that can be used in organic EL elements. The aforementioned organic material is represented by the following formula (I): Formula (I) wherein Ring A represents a phenyl group and a fused ring hydrocarbon unit having two to four ring groups, and L represents a single bond, a substituted or unsubstituted divalent subunit having 6 to 30 ring carbon atoms. An aryl group (divalent arylene group) or a substituted or unsubstituted divalent heteroarylene group having 6 to 30 ring carbon atoms, and R ₁ to R ₃ independently represent selected from the group consisting of a hydrogen atom , Substituted or unsubstituted alkyl groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted groups having 6 to 30 carbon atoms Substituted aralkyl and substituted or unsubstituted heteroaryl having 6 to 30 carbon atoms, Y ₁ to Y ₅ each independently represent a nitrogen atom or CR ₅ , R ₅ independently represents a hydrogen atom, and has 6 A substituted or unsubstituted phenylene group to 30 carbon atoms or a bond to B, B is represented by the following formula (II): Formula (II) wherein q represents an integer of 0 to 3, p represents an integer of 0 to 7, X represents O, S, NR ₆ , and R ₆ independently represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted Or an unsubstituted carbazolyl group and a bond to formula (I), R ₄ has the same definition as R ₁ .

The above description is only the preferred embodiments of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as above with the preferred embodiments, it is not intended to limit the present invention. Generally, a person skilled in the art can use the technical content disclosed above to make some changes or modify the equivalent embodiments without departing from the scope of the technical solution of the present invention. Technical essence of the invention Any simple modifications, equivalent changes, and modifications made to the above embodiments still fall within the scope of the technical solution of the present invention.

6‧‧‧ transparent electrode
7‧‧‧ Hole injection layer
8‧‧‧ Hole Transmission Layer
9‧‧‧ emitting layer
10‧‧‧ Hole barrier
11‧‧‧ electron transmission layer
12‧‧‧ electron injection layer
13‧‧‧metal electrode

FIG. 1 shows an example of the organic EL element of the present invention. 6 is a transparent electrode, 13 is a metal electrode, 7 is a hole injection layer deposited on 6, 8 is a hole transport layer deposited on 7, and 9 is a fluorescent or phosphorescent light-emitting layer deposited on 8. 10 is a hole blocking layer deposited on 9, 11 is an electron transport layer deposited on 10, and 12 is a hole injection layer deposited on 11.

6‧‧‧ transparent electrode

7‧‧‧ Hole injection layer

8‧‧‧ Hole Transmission Layer

9‧‧‧ emitting layer

10‧‧‧ Hole barrier

11‧‧‧ electron transmission layer

12‧‧‧ electron injection layer

13‧‧‧metal electrode

Claims (16)

An organic material represented by the following formula (I): Where ring A represents a phenyl group and a fused ring hydrocarbon unit having two to four ring groups, and L represents a single bond, a substituted or unsubstituted divalent arylene group having 6 to 30 ring carbon atoms arylene group) or substituted or unsubstituted divalent heteroarylene having 6 to 30 ring carbon atoms, and R ₁ to R ₃ independently represent a group selected from the group consisting of a hydrogen atom, having 6 to Substituted or unsubstituted alkyl groups of 30 carbon atoms, substituted or unsubstituted aryl groups of 6 to 30 carbon atoms, substituted or unsubstituted aralkyl groups of 6 to 30 carbon atoms And substituted or unsubstituted heteroaryl groups having 6 to 30 carbon atoms, Y ₁ to Y ₅ each independently represent a nitrogen atom or CR ₅ , and R ₅ independently represents a hydrogen atom and has 6 to 30 carbons An atom's substituted or unsubstituted phenylene group or a bond to B, B is represented by the following formula (II): Where q represents an integer of 1 to 3, p represents an integer of 0 to 7, X represents O, S, NR ₆ , and R ₆ independently represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted R ₄ has the same definition as R ₁ and a carbazolyl group and a bond to formula (I). The organic material according to claim 1, wherein L is composed of: The organic material according to claim 1, wherein the ring A is composed of naphthyl, anthracenyl, phenanthryl, fluorenyl, chrysyl, and triphenylene. An organic material represented by the following formula (I): Where ring A represents a phenyl group and a fused ring hydrocarbon unit having two to four ring groups, and L represents a single bond, a substituted or unsubstituted divalent arylene group having 6 to 30 ring carbon atoms arylene group) or substituted or unsubstituted divalent heteroarylene having 6 to 30 ring carbon atoms, and R ₁ to R ₃ independently represent a group selected from the group consisting of a hydrogen atom, having 6 to Substituted or unsubstituted alkyl groups of 30 carbon atoms, substituted or unsubstituted aryl groups of 6 to 30 carbon atoms, substituted or unsubstituted aralkyl groups of 6 to 30 carbon atoms And substituted or unsubstituted heteroaryl groups having 6 to 30 carbon atoms, Y ₁ to Y ₅ each independently represent a nitrogen atom or CR ₅ , and R ₅ independently represents a hydrogen atom and has 6 to 30 carbons An atom's substituted or unsubstituted phenylene group or a bond to B, B is represented by the following formula (II): Where q represents an integer from 0 to 3, p represents an integer from 0 to 7, X represents O, S, NR ₆ , and R ₆ independently represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted Carbazolyl and a bond to formula (I), R ₄ has the same definition as R ₁ ; wherein the organic material having formula (I) is: as well as An organic electroluminescent device includes a pair of electrodes composed of an anode and a cathode, and includes at least one light-emitting layer and one or more organic thin-film layers between the electrodes, wherein the light-emitting layer or the organic thin-film layer includes the item as claimed The organic material according to 1 or 4. The organic electroluminescent device according to claim 5, wherein the light-emitting layer includes the organic material having formula (I). The organic electroluminescent device according to claim 5, wherein the light emitting layer including the organic material having the formula (I) is a phosphorescent host material or a thermally activated delayed fluorescent host material. The organic electroluminescent device according to claim 5, wherein the light emitting layer comprises a phosphorescent dopant or a thermally activated delayed fluorescent dopant. The organic electroluminescent device according to claim 8, wherein the phosphorescent dopant is an iridium complex. The organic electroluminescent device according to claim 5, wherein the organic thin film layer is an electron transport layer, and the electron transport layer includes the organic material having the formula (I). The organic electroluminescent device according to claim 10, wherein the electron transport layer includes lithium, calcium, or lithium 8-quinolinol. The organic electroluminescent device according to claim 5, wherein the organic thin film layer is a hole blocking layer, and the hole blocking layer includes the organic material having the formula (I). The organic electroluminescent device according to claim 5, wherein the light emitting layer emits green, yellow, and red phosphorescence. The organic electroluminescent device according to claim 5, wherein the device is an organic light emitting device. The organic electroluminescent device according to claim 5, wherein the device is a light-emitting flat plate. The organic electroluminescent device according to claim 5, wherein the device is a backlight panel.