CN109678875B - Phosphorescent compound and organic light emitting diode device using same - Google Patents
Phosphorescent compound and organic light emitting diode device using same Download PDFInfo
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Abstract
The present invention relates to a phosphorescent compound and an organic light emitting diode device using the same, and more particularly, to a soluble phosphorescent host compound having excellent color purity and high luminance and light emitting efficiency and an OLED device using the same. A phosphorescent compound characterized by: the structural formula is shown as I,
in the above formula I, Z is independently selected from the following structures:
wherein Ar is independently selected from a C6-C30 aryl group and a C2-C30 heteroaryl group, the C6-C30 aryl group is selected from one of phenyl, naphthyl, biphenyl, terphenyl and phenanthryl, and the C2-C30 heteroaryl group is selected from one of pyridyl, bipyridyl, quinolyl, isoquinolyl, phenanthrolinyl and triazinyl. The present invention uses the chemical formula shown in I as a light emitting layer of an organic light emitting diode device, and has excellent color purity and brightness and a prolonged durability effect.
Description
Technical Field
The present invention relates to a phosphorescent compound and an organic light emitting diode device using the same, and more particularly, to a soluble phosphorescent host compound having excellent color purity and high luminance and light emitting efficiency and an OLED device using the same.
Background
Recently, the demand for flat panel displays (e.g., liquid crystal displays and plasma display panels) is increasing. However, these flat panel displays have a lower response time and a narrower viewing angle than Cathode Ray Tubes (CRTs).
An Organic Light Emitting Diode (OLED) device is one of the next generation flat panel displays that can solve the above problems and occupy a small area.
The elements of the OLED device may be formed on a flexible substrate, such as a plastic substrate. In addition, OLED devices have advantages in view angle, driving voltage, power consumption, and color purity. Outside, the OLED device is sufficient to produce full color images.
In general, a light emitting diode of an OLED device includes an anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Emitting Material Layer (EML), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode.
The OLED device emits light by: electrons and holes are injected into the light emitting compound layer from the cathode as an electron injection electrode and from the anode as a hole injection electrode, respectively, so that the electrons and the holes are recombined to generate excitons, and the excitons are made to transition from an excited state to a ground state.
The principle of luminescence can be divided into fluorescence and phosphorescence. In fluorescence emission, an organic molecule in a singlet excited state transits to a ground state, thereby emitting light. On the other hand, in phosphorescence, organic molecules in a triplet excited state transition to a ground state, thereby emitting light.
When the light emitting material layer emits light corresponding to the energy band gap, singlet excitons having 0 spin and triplet excitons having 1 spin are generated in a ratio of 1: 3. The ground state of the organic material is a singlet state, which allows singlet excitons to transition to the ground state with accompanying light emission. However, since the triplet exciton cannot undergo transition accompanying light emission, the internal quantum efficiency of the OLED device using the fluorescent material is limited to within 25%.
On the other hand, if the spin orbit coupling momentum is high, the singlet state and the triplet state are mixed so that an intersystem crossing occurs between the singlet state and the triplet state, and the triplet exciton may also transition to the ground state with emission of light. The phosphorescent material may use triplet excitons and singlet excitons, so that an OLED device using the phosphorescent material may have an internal quantum efficiency of 100%.
Recently, iridium complexes, such as bis (2-phenylquinoline) (acetylacetonate) iridium (iii) (Ir (2-phq)2(acac)), bis (2-benzo [ b ] thiophen-2-ylpyridine) (acetylacetonate) iridium (iii) (Ir (btp)2(acac)), and tris (2-phenylquinoline) iridium (iii) Ir (2-phq)3 dopants have been introduced.
In order to obtain high current luminous efficiency (Cd/a) using a phosphorescent material, excellent internal quantum efficiency, high color purity, and long lifetime are required. In particular, referring to fig. 1, the higher the color purity, i.e., the higher cie (x), the worse the color sensitivity. As a result, it is very difficult to obtain light emission efficiency at high internal quantum efficiency. Therefore, there is a need for novel red phosphorescent compounds having excellent color purity (CIE (X) ≥ 0.65) and high luminous efficiency.
On the other hand, in addition to the iridium complex described above, for example, 4,4-N, N Carbazole Biphenyl (CBP) or other metal complexes are used as the red phosphorescent compound. However, these compounds do not have ideal solubility in a solvent, and thus cannot form a light emitting layer by a solution process. The light emitting layer should be formed through a deposition process, and thus, the manufacturing process is very complicated and the process efficiency is very low. In addition, the waste material in the deposition process is very large, resulting in increased production costs.
Disclosure of Invention
The present invention is directed to providing a phosphorescent compound and an organic light emitting diode device using the same to solve the disadvantages of the prior art.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a phosphorescent compound has a structural formula shown as I,
in the structural formula I, R is independently selected from the following structures:
wherein Ar is independently selected from the group consisting of C6-C30 aryl, C2-C30 heteroaryl.
Further, the C6-C30 aryl is selected from one of phenyl, naphthyl, biphenyl, terphenyl and phenanthryl.
Further, the C2-C30 heteroaryl is selected from one of pyridyl, bipyridyl, quinolyl, isoquinolyl, phenanthrolinyl and triazinyl.
Further, Ar is independently selected from one of the following groups: (any of the following groups may be substituted for a position originally having an active hydrogen atom)
Further, the phosphorescent compound is independently selected from the following compounds:
further, the organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode which are deposited in sequence, and the phosphorescent compound is used as a main material of the light emitting layer.
The invention has the advantages that: the present invention uses the chemical formula shown in I as a light emitting layer of an organic light emitting diode device, and has excellent color purity and brightness and a prolonged durability effect.
Drawings
FIG. 1 is a graph of chromaticity and visibility of light emitted from an organic electroluminescent diode.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further described with reference to the figures and the specific embodiments.
As the red phosphorescent compounds with the structural formula I all have excellent pure chromaticity, high brightness and excellent luminous efficiency, the technical scheme and the achieved technical effect provided by the invention are proved by taking RH-001, RH-007, RH-091 and RH-097 preparation methods and test results as examples.
In the following embodiments, NPB is 4,4 ' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl, CBP is 4,4 ' -N, N ' -dicarbakisbiphenyl, CuPc is copper phthalocyanine, LiF lithium fluoride, ITO is indium tin oxide, and Alq3 is tris (8-hydroxyquinoline) aluminum.
LC-MS, liquid chromatography-mass spectrometer, M/Z: ratio of number of protons/number of charges.
The following formulae are structural formulae for the compounds copper (II) phthalocyanine (CuPc), NPB, (btp)2Ir (acac), Alq3 and CBP used in embodiments of the present invention.
Examples of formation
1. Synthesis of intermediate I-1:
in a 1000mL flask, 5-bromo-6-fluoroindoline-2, 3-dione (50g,204.9mmol), 2-methylthiophenylboronic acid (37.9g,225.4mmol), Pd (PPh3)4(5 mol%), and potassium carbonate (70.8g, 512.3mmol) were added to a mixed solvent of THF (500mL) and water (240 mL). The reaction solution was heated to 60 ℃ under nitrogen protection and reacted for 12 hours. After completion of the reaction, the aqueous layer was removed, and the remaining organic layer was concentrated and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and filtered through silica gel/celite. After removal of the appropriate amount of organic solvent, recrystallization from methanol gave intermediate I-1(40.0g, yield 68%). LC-MS M/Z288.3 (M + H)+。
2. Synthesis of intermediate I-2:
in 1000mLIn a bottle, intermediate I-1(40g,139.2mmol) was dissolved in dichloromethane (600 mL). Boron tribromide (278.4mL, 278.4mmol) was then added dropwise while maintaining the temperature at 0 ℃. When the reaction was completed, the reaction solution was washed with an aqueous solution of sodium thiosulfate. After concentration of the organic phase, the crude product was dissolved in DMF (300mL) at room temperature without further purification, to which was added 60% sodium hydrogen (8.4g,208.8mmol) in an ice bath. The reaction was then warmed to 100 ℃ and stirred for 1h, cooled to room temperature and dropped into 800mL of water. The resulting solid was filtered and recrystallized from methanol to give intermediate I-2(27.5g, yield 78%). LC-MS M/Z253.28 (M + H)+。
3. Synthesis of intermediate I-3:
intermediate I-2(27g,106.6mmol) and 1.0N aqueous sodium hydroxide solution (200mL) were charged into a 1000mL flask, then warmed to 80 ℃ under a stream of nitrogen and stirred. 20% hydrogen peroxide (16.7mL) was added dropwise thereto through a dropping funnel for 30 minutes, and the resulting mixture was stirred at 80 ℃ for 1 hour. The reaction was cooled to-10 ℃ and concentrated. Subsequently, HCl was slowly added thereto to adjust the pH of the reaction solution in the range of 4 to 5, the reaction solution was concentrated again, and methanol (400mL) was added thereto, and the resulting mixture was stirred for 15 minutes and filtered, and the filtrate was dried to give intermediate I-3(24.6g), which was used without further purification.
4. Synthesis of intermediate I-4:
intermediate I-3(24g,98.7mmol) and urea (59.3g,986.2mmol) were placed in a 500mL flask, which was then heated to 180 ℃ for 12 hours under a stream of nitrogen. When the reaction of intermediate I-3 was completed, the temperature was slightly lowered, and o-dichlorobenzene (100mL) and water (600mL) were added thereto and stirred. The resulting solid was filtered and dried to give intermediate I-4(15.9g, yield 60%). LC-MS M/Z269.3 (M + H)+。
5. Synthesis of intermediate I-5:
in a 500mL flask, intermediate I-4(15g,55.9mmol) was dissolved in phosphorus oxychloride (52.2g, 391.4mmol), and the mixture was heated to 120 ℃ for 4 hours under a stream of nitrogen. The reaction mixture was poured slowly into a large amount of ice, and the resulting solid was filtered, washed with water and methanol, and dried to give intermediate I-5(13.1g, yield 77%). LC-MS M/Z306.2 (M + H)+。
6. Synthesis of intermediate I-6:
a500 mL reaction flask was charged with I-5(10.0g,32.8mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid (9.4g,32.8mmol), potassium carbonate (11.3g,81.9mmol), tetrakistriphenylphosphine palladium (5 mol%), 1, 4-dioxane (140mL) and water (70 mL). The reaction system is heated to 60 ℃ and reacts for ten hours under the protection of nitrogen. The reaction solution was poured into 450mL of methanol, and the precipitated solid was filtered. The precipitated solid was dissolved in chlorobenzene and filtered through a funnel containing celite and silica gel powder. The orange liquid obtained by filtration was concentrated to dryness and recrystallized from methanol to obtain intermediate I-6(11.1g, yield 66%). LC-MS: M/Z513.0 (M + H))+。
Synthesis of RH-001:
a250 ml three-necked flask was charged with intermediate I-6(5g,9.8mmol), 7H-dibenzo [ c, g)]Carbazole (2.9g,10.7mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (3.3g,329.3mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 12 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. Organic layerThe crude product was dried over anhydrous magnesium sulfate, concentrated and recrystallized to give RH-001(5.7g, yield 78%). LC-MS: M/Z743.9 (M + H)+。
8. Synthesis of intermediate I-7:
a500 mL reaction flask was charged with I-5(10.0g,32.8mmol), carbazole 9- (4-biphenyl) -3-borate (11.9g,32.8mmol), potassium carbonate (11.3g,81.9mmol), tetrakis triphenylphosphine palladium (5 mol%), 1, 4-dioxane (140mL) and water (70 mL). The temperature of the reaction system is raised to 60 ℃, and the reaction is carried out for ten hours under the protection of nitrogen. The reaction solution was poured into 450mL of methanol, and the precipitated solid was filtered. The precipitated solid was dissolved in chlorobenzene and filtered through a funnel containing celite and silica gel powder. The orange liquid obtained by filtration was concentrated to dryness and recrystallized from methanol to give intermediate I-7(11.2g, yield 58%) LC-MS: M/Z589.1 (M + H))+。
Synthesis of RH-007:
a250 ml three-necked flask was charged with intermediate I-7(5g,8.5mmol), 7H-dibenzo [ c, g]Carbazole (2.5g,9.4mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (2.9g,25.5mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 12 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give RH-007(5.3g, yield 76%). LC-MS: M/Z820.0 (M + H)+。
10. Synthesis of intermediate I-8:
intermediate I-5 (1) was added to a 500ml reaction flask0.0g,32.8mmol), (9-phenyl-9H-carbazol-2-yl) boronic acid (9.4g,32.8mmol), potassium carbonate (11.3g,81.9mmol), palladium tetrakistriphenylphosphine (5 mol%), 1, 4-dioxane (140mL) and water (70 mL). The reaction system is heated to 60 ℃ and reacts for ten hours under the protection of nitrogen. The reaction solution was poured into 450mL of methanol, and the precipitated solid was filtered. The precipitated solid was dissolved in chlorobenzene and filtered through a funnel containing celite and silica gel powder. The orange liquid obtained by filtration was concentrated to dryness and recrystallized from methanol to yield intermediate I-8(11.4g, yield 68%) LC-MS: M/Z513.0 (M + H))+。
Synthesis of RH-091:
a250 ml three-necked flask was charged with intermediate I-8(5g, 9.8mmol), 7H-dibenzo [ c, g]Carbazole (2.9g,10.7mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (3.3g,25.2mmol) and o-xylene (80 mL). The temperature of the reaction system is raised to 120 ℃, and the reaction is carried out for 12 hours under the protection of nitrogen. After the reaction was completed, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give crude product which was then passed through a silica gel column to give RH-091(6.0g, yield 83%). LC-MS: M/Z743.9 (M + H)+。
12. Synthesis of intermediate I-9:
a500 mL reaction flask was charged with I-5(10.0g,32.8mmol), carbazole 9- (4-biphenyl) -2-borate (11.9g,32.8mmol), potassium carbonate (11.3g,81.9mmol), tetrakis triphenylphosphine palladium (5 mol%), 1, 4-dioxane (140mL) and water (70 mL). The temperature of the reaction system is raised to 60 ℃, and the reaction is carried out for ten hours under the protection of nitrogen. The reaction solution was poured into 450mL of methanol, and the precipitated solid was filtered. The precipitated solid was dissolved in chlorobenzene and filtered through a funnel containing celite and silica gel powder. The orange liquid obtained by filtration was concentrated to dryness and recrystallized from methanol to give intermediate I-9(11.6g, yield 60%) LC-MS:M/Z 589.1(M+H)+。
synthesis of RH-097:
a250 ml three-necked flask was charged with intermediate I-9(5g,8.5mmol), 7H-dibenzo [ c, g]Carbazole (2.5g,9.4mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (2.9g,25.5mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 12 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give RH-007(5.7g, yield 82%). LC-MS: M/Z820.0 (M + H)+。
Detailed description of the preferred embodiments
1. First embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, CuPc was applied onto the ITO substrate
NPB
RH-001+(btp)2Ir(acac)((5％)
Alq3 
LiF
And Al
The sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the luminance is equal to 1224cd/m2(5.9V). In this case, CIEx is 0.659 and y is 0.331.
2. Second embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, CuPc was applied onto the ITO substrate
NPB
RH-007+(btp)2Ir(acac)(5％)
Alq3 
LiF
And Al
The sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the luminance is equal to 1142cd/m2(6.1V). In this case, CIEx is 0.660 and y is 0.330.
3. Third embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, CuPc was applied onto the ITO substrate
NPB
RH-091+(btp)2Ir(acac)(5％)
Alq3 
LiF
And Al
The sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the luminance is equal to 1203cd/m2(6.0V). In this case, CIEx is 0.658 and y is 0.330.
4. Fourth embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, CuPc was applied onto the ITO substrate
NPB
RH-097+(btp)2Ir(acac)(5％)
Alq3 
LiF
And Al
The sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the luminance is equal to 1109cd/m2(6.2V). In this case, CIEx is 0.660 and y is 0.329.
5. Comparative example
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Using CuPc on ITO substrate
NPB
CPB+(btp)2Ir(acac)(5％)
Alq3 
LiF
And Al
The sequence of (a) to (b) forms a layer of organic material.
At 0.9mA, the luminance is equal to 780cd/m2(7.5V). In this case, CIEx is 0.659 and y is 0.329.
It is shown in fig. 1 that the color purity of the organic electroluminescent device increases (i.e., the X value becomes larger as the chromaticity coordinate becomes larger) and the visibility decreases.
The characteristics of efficiency, chromaticity coordinates, and luminance according to the above-described embodiments and comparative examples are shown in table 1 below.
TABLE 1
As shown in table 1, the device operates at high efficiency at low voltage even when the color purity is high. Also, the current efficiency of the second embodiment is increased by 50% or more compared to the comparative example.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (2)
1. A phosphorescent compound selected from the following compounds:
2. an organic light-emitting diode device using the phosphorescent compound according to claim 1, wherein: the organic light-emitting diode device sequentially comprises a deposited anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode, and the phosphorescent compound is used as a main material of the light-emitting layer.
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| CN109678867B (en) * | 2018-11-08 | 2022-05-20 | 浙江华显光电科技有限公司 | Phosphorescent compound and organic light emitting diode device using the same |
| CN109438468A (en) * | 2018-11-26 | 2019-03-08 | 浙江华显光电科技有限公司 | A kind of phosphorescence host compound and its organic electroluminescence device using the compound |
| CN110330481B (en) * | 2019-07-03 | 2022-04-08 | 浙江华显光电科技有限公司 | Red phosphorescent compound and organic light-emitting device using same |
| CN110951482A (en) * | 2019-10-23 | 2020-04-03 | 宇瑞(上海)化学有限公司 | Phosphorescent compound and organic electroluminescent device using same |
| CN111423447A (en) * | 2019-10-23 | 2020-07-17 | 宇瑞(上海)化学有限公司 | Red phosphorescent compound and organic light-emitting device |
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