CN111454244B - Compound, display panel and display device - Google Patents
Compound, display panel and display device Download PDFInfo
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- CN111454244B CN111454244B CN202010238480.0A CN202010238480A CN111454244B CN 111454244 B CN111454244 B CN 111454244B CN 202010238480 A CN202010238480 A CN 202010238480A CN 111454244 B CN111454244 B CN 111454244B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K50/17—Carrier injection layers
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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Abstract
The application belongs to the technical field of OLED (organic light emitting diode), and discloses a compound containing an oxaanthracene group and a diarylamino group, which has a structure shown in a formula 1. The diarylamine compound can be used as a hole transport material of aromatic amine aromatic rings and weak electron donating groups, has shallower LUMO and proper HOMO values, and can effectively block electron transition. The compounds of the invention have a higher triplet energy level E T The exciton can be effectively blocked from being transmitted, the exciton is limited in the light-emitting layer, and the transmission of holes is improved; the high electron mobility, excellent thermal stability and film stability are realized, and the luminous efficiency and the service life of the device are improved. The invention also provides a display panel and a display device.
Description
Technical Field
The application relates to the technical field of organic electroluminescent materials, in particular to a diarylamine compound, and a display panel and a display device containing the diarylamine compound.
Background
Many small and medium-sized OLED screens of mobile phone consumer products and the like adopt a R, G, B sub-pixel display mode. To increase the production yield, some functional layers are often designed as common layers, so that FFM (fine metal mask) can be used less, whereas hole transport layers are often common layers, and common hole transport layers can be made of commercially available materials. Commercially available hole transport layer materials such as compound 1 (EP-721935) have a relatively high mobility in the machine direction and a relatively low mobility in the transverse direction, and Cross talk between pixels does not occur.
Patent CN103108859 discloses that compound 2, the material has better solubility properties, while the mobility is higher.
The existing hole transport material technology has the following problems, firstly, poor material solubility can cause poor cleaning effect of evaporation Mask during mass production. Second, the mobility of the material is too slow, which can result in too high an overall voltage of the device. Third, the mobility of the material, and especially the lateral mobility of the material, is too fast, resulting in cross-talk of adjacent pixels. Fourth, the LUMO level of the material is too deep to effectively block electron migration that may pass over the light emitting layer. Fifth, the triplet state energy level of the material is low, and the transmission of holes in RGB three colors can not be realized at the same time, so that the number of masks is increased, and the process difficulty is improved.
The mobility of the commercial materials in patent EP-721935 is in an acceptable range, cross talk does not occur, but the solubility is not very good and the triplet state is not too high. The commercial material of patent CN103108859 can dissolve but mobility is too fast, resulting in lateral leakage currents and cross talk.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a diarylamine compound having a structure represented by formula 1:
L 1 selected from the group consisting of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C12-C40 fused arylene group, a C5-C30 heteroarylene group, a C8-C40 fused heteroarylene group;
a has a structure represented by formula 2:
L 2 selected from single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C12-C40 fused arylene, substituted or unsubstitutedUnsubstituted C3-C30 heteroarylene, substituted or unsubstituted C6-C40 heteroarylene;
L 3 selected from the group consisting of substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C12-C40 fused arylene, substituted or unsubstituted C3-C30 heteroarylene, and substituted or unsubstituted C6-C40 fused heteroarylene;
Ar 1 selected from diarylamino groups;
Ar 2 and Ar is a group 3 Each independently selected from C6-C30 aryl, diarylamino substituted C6-C30 aryl;
# denotes a connection position.
The compound can be used as a hole type transmission material, the structure of the compound contains diarylamino related to the traditional hole type material, and the LUMO energy level of the material can be effectively regulated. The compound structure contains relatively weaker electron donating groups, has deeper HOMO energy level, and can effectively improve the hole transmission capability. The diarylamine compound has high triplet state energy level, can effectively block the transmission of excitons, limit the excitons in a light-emitting layer, and improve the efficiency of the device; the pixel-to-pixel crosstalk can be effectively avoided due to the proper mobility; the proper twisting and steric hindrance between groups in the molecule can lead the material to have better solubility.
The diarylamine compound has high electron mobility, excellent thermal stability and film stability, and is beneficial to improving the luminous efficiency and prolonging the service life of devices.
Drawings
FIG. 1 shows the chemical structure of an exemplary compound HT1 of the present invention;
FIG. 2 is a schematic diagram of an OLED device according to an embodiment of the present invention;
fig. 3 is a schematic diagram of a display device according to an embodiment of the invention.
Detailed Description
The present invention is further illustrated by the following examples and comparative examples, which are only for illustration of the present invention, and the present invention is not limited to the following examples. All modifications and equivalent substitutions to the technical proposal of the invention are included in the protection scope of the invention without departing from the scope of the technical proposal of the invention.
The object of the present invention is to provide a diarylamine compound having a structure represented by formula 1:
L 1 selected from the group consisting of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C12-C40 fused arylene group, a C5-C30 heteroarylene group, a C8-C40 fused heteroarylene group;
a has a structure represented by formula 2:
L 2 selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C12-C40 fused arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, a substituted or unsubstituted C6-C40 fused heteroarylene group;
L 3 selected from the group consisting of substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C12-C40 fused arylene, substituted or unsubstituted C3-C30 heteroarylene, and substituted or unsubstituted C6-C40 fused heteroarylene;
Ar 1 selected from diarylamino groups;
Ar 2 and Ar is a group 3 Each independently selected from C6-C30 aryl, diarylamino substituted C6-C30 aryl;
# denotes a connection position.
The compound of the invention can be used as a hole transport material of an OLED device, and as a pure hole transport material, the material is required to have relatively strong electron-donating ability so as to promote effective injection and transport of holes. The inventors of the present invention found that the larger the number of adjacently connected diarylamines connected to benzene rings on benzoxanthene groups, the stronger the electron donating ability of the molecule, thereby reducing the energy level barrier for anode hole injection and lowering the device driving voltage. In addition, two or more than two adjacent (serially connected) diarylamines can relieve the influence of poor molecular solubility caused by thick benzo [ kl ] oxy anthracene groups, improve the solubility of materials and reduce the difficulty of mask cleaning in the manufacturing process of the organic light-emitting device.
According to one embodiment of the compounds according to the invention, L 1 、L 2 And L 3 Each independently selected from any one of the groups shown below:
wherein Z is 1 And Z 2 Each independently selected from at least one of a hydrogen atom, a halogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C10-C30 condensed aryl group;
p and q are each independently selected from 0, 1, 2, 3 or 4;
# denotes a connection position.
In this embodiment, the linking group is selected from an aromatic or heteroaromatic ring. The aromatic or heteroaromatic ring groups are stable per se and have good electrochemical and thermal stability. In the running process of the device, the degradation or decomposition of materials is not caused, and the risk of the service life of the device is avoided. Other common groups, such as alkyl groups, alkenyl groups and the like, have poor structural stability, and during the operation of the device, vibration relaxation among molecules is large, and meanwhile, molecules can be decomposed, so that the service life of the device is reduced.
According to one embodiment of the compounds according to the invention, L 1 、L 2 And L 3 Each independently selected from any one of the groups shown below:
# denotes a connection position.
According to one embodiment of the compounds of the invention, the compounds are selected from the following compounds:
according to one embodiment of the compounds according to the invention, the triplet energy level E of the compounds T Is 2.6eV or more. The compound provided by the invention has a high triplet state energy level, can effectively block the transmission of excitons, limit the excitons in a light-emitting layer, and prevent the loss of the excitons, thereby improving the light-emitting efficiency of the device.
According to the invention of the compoundsIn one embodiment, the compound has a glass transition temperature T g Is above 120deg.C.
The present invention also provides a display panel comprising an organic light emitting device comprising an anode, a cathode, at least one organic compound layer between the anode and the cathode, wherein the organic compound of the organic compound layer comprises at least one of the compounds of the present invention.
According to an embodiment of the display panel of the present invention, the organic compound layer includes a hole transport layer including at least one of the compounds of the present invention.
According to an embodiment of the display panel of the present invention, the organic compound layer includes a hole injection layer including at least one of the compounds of the present invention.
In the display panel provided by the present invention, the anode material of the organic light emitting device may be selected from metals such as copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof. The anode material may also be selected from metal oxides such as indium oxide, zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and the like; the anode material may also be selected from conductive polymers such as polyaniline, polypyrrole, poly (3-methylthiophene), and the like. In addition, the anode material may be selected from materials other than the anode materials listed above that facilitate hole injection, and combinations thereof, including materials known to be suitable as anodes.
In the display panel provided by the present invention, the cathode material of the organic light emitting device may be selected from metals such as aluminum, magnesium, silver, indium, tin, titanium, etc., and alloys thereof. The cathode material may also be selected from multi-layered metallic materials such as LiF/Al, liO 2 /Al、BaF 2 Al, etc. In addition to the cathode materials listed above, the cathode materials may also be materials that facilitate electron injection and combinations thereof, including materials known to be suitable as cathodes.
In an embodiment of the present invention, the manufacturing process of the organic light emitting device is: an anode is formed on a transparent or opaque smooth substrate, an organic thin film layer is formed on the anode, and a cathode is formed on the organic thin film layer. The organic thin film layer may be formed by a known film formation method such as vapor deposition, sputtering, spin coating, dipping, ion plating, and the like. The organic film layer at least comprises a hole transport layer and a luminescent layer, and the hole transport layer is made of the compound disclosed by the invention. Wherein the organic film layer can also comprise an electron blocking layer, and the material of the electron blocking layer is the compound of the invention.
Another aspect of the invention illustratively describes the synthesis of compounds HT1, HT2, HT3, HT8, HT16, HT21, HT45, HT49 and HT61.
Example 1
3-chloro-benzo [ kl ] in 250ml round bottom flask]Xanthene (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and 4-bromo-diphenyl-amine (20 mmol) were added to dry 1, 4-dioxane (100 mL), in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give intermediate HT1-1.
In a 250ml round bottom flask, the intermediate HT1-1 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and diphenylamine (20 mmol) were added to dry 1, 4-dioxane (100 ml), under N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give the final product HT1.
Elemental analysis results of Compound HT1 (formula C 40 H 28 N 2 O): theoretical value: c,86.93; h,5.11; n,5.07; o,2.89. Test value: c,86.39; h,5.31; n,5.36; o,2.94. Analysis by liquid phase Mass SpectrometryObtaining ESI-MS (M/z) (M) + ): theoretical 552.68 and test 552.78.
Example 2
9-chloro-benzo [ kl ] in 250ml round bottom flask]Xanthene (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and 3-bromo-diphenyl-amine (20 mmol) were added to dry 1, 4-dioxane (100 mL), in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by column chromatography on silica gel to give intermediate HT2-1.
In a 250ml round bottom flask, the intermediate HT2-1 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and diphenylamine (20 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give the final product HT2.
Elemental analysis results of Compound HT2 (formula C 40 H 28 N 2 O): theoretical value: c,86.93; h,5.11; n,5.07; o,2.89. Test value: c,86.39; h,5.31; n,5.33; o,2.97. ESI-MS (M/z) (M) was obtained by liquid phase mass spectrometry + ): theoretical 552.68 and test 552.78.
Example 3
4-chloro-benzo [ kl ] in a 250ml round bottom flask]Xanthene (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and 4-bromo-diphenyl-)Amine (20 mmol) was added to dry 1, 4-dioxane (100 ml), at N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give intermediate HT3-1.
In a 250ml round bottom flask, the intermediate HT3-1 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and diphenylamine (20 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give the final product HT3.
Elemental analysis results of Compound HT3 (formula C 40 H 28 N 2 O): theoretical value: c,86.93; h,5.11; n,5.07; o,2.89. Test value: c,86.39; h,5.27; n,5.40; o,2.94. ESI-MS (M/z) (M) was obtained by liquid phase mass spectrometry + ): theoretical 552.68 and test 552.43.
Example 4
3-chloro-benzo [ kl ] in 250ml round bottom flask]Xanthene (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and 3-bromo-diphenyl-amine (20 mmol) were added to dry 1, 4-dioxane (100 mL), in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give intermediate HT8-1.
In a 250ml round bottom flask, intermediate HT8-1 (15 mmol), cuprous iodide (15 mmol)Potassium tert-butoxide (65 mmol) and diphenylamine (20 mmol) were added to dry 1, 4-dioxane (100 mL), at N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give the final product HT8.
Elemental analysis results of Compound HT8 (formula C 40 H 28 N 2 O): theoretical value: c,86.93; h,5.11; n,5.07; o,2.89. Test value: c,86.39; h,5.41; n,5.46; o,2.74. ESI-MS (M/z) (M) was obtained by liquid phase mass spectrometry + ): theoretical 552.68 and test 552.78.
Example 5
9-chloro-benzo [ kl ] in 250ml round bottom flask]Xanthene (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and 3-bromo-diphenyl-amine (20 mmol) were added to dry 1, 4-dioxane (100 mL), in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give intermediate HT16-1.
In a 250ml round bottom flask, the intermediate HT16-1 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and diphenylamine (20 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give the final product HT16.
Elemental analysis results (molecular) of Compound HT16C (C) 40 H 28 N 2 O): theoretical value: c,86.93; h,5.11; n,5.07; o,2.89. Test value: c,86.39; h,5.41; n,5.51; o,2.69. ESI-MS (M/z) (M) was obtained by liquid phase mass spectrometry + ): theoretical 552.68 and test 552.78. Supplementing nuclear magnetic data, checking molecular formula and element analysis value
Example 6
4-boronic acid-benzo [ kl ] in a 250mL round bottom flask]Xanthene (15 mmol), 1, 4-dichloro-benzene (15 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH (absolute ethanol)/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while being extracted with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate HT21-1.
In a 250ml round bottom flask, the intermediate HT21-1 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and 4-bromodiphenyl-amine (20 mmol) were added to dry 1, 4-dioxane (400 ml) in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give intermediate HT21-2.
In a 250ml round bottom flask, the intermediate HT21-2 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and diphenylamine (20 mmol) were added to dry 1, 4-dioxane (400 ml) in N 2 Reflux for 48 hours under ambient conditions, the resulting intermediate was cooled to room temperature, added to water, and then filtered through a pad of celite while using dichloroMethane extraction, then washing with water, drying over anhydrous magnesium sulfate, filtration and removal of solvent, purification of the crude product by silica gel column chromatography gives the final product HT21.
Elemental analysis results of Compound HT21 (formula C 46 H 32 N 2 O): theoretical value: c,87.87; h,5.13; n,4.46; o,2.54. Test value: c,87.98; h,5.01; n,4.52; o,2.49. ESI-MS (M/z) (M) was obtained by liquid phase mass spectrometry + ): theoretical 628.78 and test 628.21.
Example 7
In a 250mL round bottom flask, 8-boronic acid-benzo [ kl]Xanthene (15 mmol), 1, 4-dichloro-benzene (15 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH (absolute ethanol)/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate HT45-1.
In a 250ml round bottom flask, the intermediate HT45-1 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and 4-bromodiphenyl-amine (20 mmol) were added to dry 1, 4-dioxane (400 ml) in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give intermediate HT45-2.
In a 250ml round bottom flask, intermediate HT45-2 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and diphenylamine (20 mmol) were added to dry 1,in 4-dioxane (400 ml), in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give the final product HT45.
Elemental analysis results of Compound HT45 (formula C 46 H 32 N 2 O): theoretical value: c,87.87; h,5.13; n,4.46; o,2.54. Test value: c,87.98; h,5.22; n,4.31; o,2.49. ESI-MS (M/z) (M) was obtained by liquid phase mass spectrometry + ): theoretical 628.78 and test 628.43.
Example 8
In a 250mL round bottom flask, 8-boronic acid-benzo [ kl]Xanthene (15 mmol), 1, 4-dichloro-benzene (15 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH (absolute ethanol)/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate HT49-1.
In a 250ml round bottom flask, the intermediate HT49-1 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and 3-bromo-diphenyl-amine (20 mmol) were added to dry 1, 4-dioxane (400 ml) in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give intermediate HT49-2.
In a 250ml round bottom flask, intermediate HT49-2 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and diphenylamine (20 mmol) were added to dry 1, 4-dioxane (400 ml) in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give the final product HT49.
Elemental analysis results of Compound HT49 (formula C 46 H 32 N 2 O): theoretical value: c,87.87; h,5.13; n,4.46; o,2.54. Test value: c,87.98; h,5.31; n,4.22; o,2.49. ESI-MS (M/z) (M) was obtained by liquid phase mass spectrometry + ): theoretical 628.78 and test 628.62.
Example 9
4-boronic acid-benzo [ kl ] in a 250mL round bottom flask]Xanthene (15 mmol), 1, 4-dichloro-benzene (15 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH (absolute ethanol)/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate HT61-1.
In a 250ml round bottom flask, the intermediate HT61-1 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and di- (4-bromo-phenyl) -amine (20 mmol) were added to dry 1, 4-dioxane (400 ml) under N 2 Reflux for 48 hours under atmosphere, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite,simultaneously extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed and the crude product purified by column chromatography on silica gel to give intermediate HT61-2.
In a 250ml round bottom flask, intermediate HT61-2 (15 mmol), cuprous iodide (15 mmol), potassium tert-butoxide (65 mmol) and diphenylamine (35 mmol) were added to dry 1, 4-dioxane (400 ml) in N 2 Reflux for 48 hours under ambient conditions, the intermediate obtained was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and the solvent removed, and the crude product purified by column chromatography on silica gel to give the final product HT61.
Elemental analysis results of Compound HT61 (formula C 58 H 41 N 3 O): theoretical value: c,87.52; h,5.19; n,5.28; o,2.01. Test value: c,87.68; h,5.21; n,5.12; o,1.99. ESI-MS (M/z) (M) was obtained by liquid phase mass spectrometry + ): theoretical 795.99 and test 796.09.
Table 1 below sets forth the HOMO values, LUMO values, energy level differences E of the compounds HT1, HT2, HT3, HT8, HT16, HT21, HT45, HT49 and HT61, and of the comparative examples HT-Ref g Triplet energy level (E T )。
Energy level values of the compounds of Table 1
As can be seen from table 1 above, the compounds prepared in the examples of the present invention can be used as hole transport materials, and compared with the comparative examples HT-ref, the materials HT1, HT2, HT3, HT8, HT16, HT21, HT45, HT49 and HT61 of the present invention have shallower HOMO level values and appropriate LUMO level values, reducing the energy level barrier for hole injection in the anode direction, thereby reducing the driving voltage of the entire device; the hole injection is facilitated, the balance transmission of holes and electrons is improved, and the device performance is improved.
Device example 1
The present embodiment provides an OLED device, as shown in fig. 1, including: the substrate 1, the ITO anode 2, the first hole transporting layer 3, the second hole transporting layer 4, the electron blocking layer 5, the light emitting layer 6, the first electron transporting layer 7, the second electron transporting layer 8, the cathode 9 (magnesium silver electrode) and the capping layer 10, wherein the thickness of the ITO anode 2 is 10nm, the thickness of the first hole transporting layer 3 is 10nm, the thickness of the second hole transporting layer 4 is 95nm, the thickness of the electron blocking layer is 30nm, the thickness of the light emitting layer 6 is 30nm, the thickness of the first electron transporting layer 7 is 30nm, the thickness of the second electron transporting layer 8 is 5nm, the thickness of the magnesium silver electrode 9 is 15nm, and the thickness of the capping layer 10 is 100nm.
The OLED device of the invention is prepared by the following steps:
1) Cutting the glass substrate 1 into 50mm×50mm×0.7mm sizes, respectively sonicating in isopropyl alcohol and deionized water for 30 minutes, and then exposing to ozone for about 10 minutes for cleaning; mounting the obtained glass substrate 1 having the ITO anode 2 onto a vacuum deposition apparatus;
2) At a vacuum degree of 2X 10 -6 Evaporating a hole injection layer material HT 1:HAT-CN on an ITO anode layer 2 in a vacuum evaporation mode under Pa, wherein the mass ratio of the compound HT1 to the HAT-CN is 98:2, so as to obtain a layer with the thickness of 10nm, and the layer is used as a first hole transport layer 3;
3) Vacuum evaporating the material HT1 of the present invention with a thickness of 95nm on the first hole transport layer 3 as the second hole transport layer 4;
4) Vacuum evaporating an electron blocking layer 5 on the second hole transport layer 4, wherein the material of the electron blocking layer 5 is Prime-1, and the thickness of the electron blocking layer is 30nm, and the electron blocking layer 5 is formed;
5) A light-emitting layer 6 is co-deposited on the electron blocking layer 5, the host material of the light-emitting layer 6 is BH, the guest material is BD-1, the mass ratio of the compound BH to BD-1 is 97:3, and the thickness is 30nm;
6) Vacuum evaporating a first electron transport layer 7 on the light-emitting layer 6, wherein the material of the first electron transport layer 7 is ET-1, and the thickness is 30nm;
7) Vacuum evaporating a second electron transport layer 8 on the first electron transport layer 7, wherein the material of the second electron transport layer 8 is LiF, and the thickness is 5nm;
8) Vacuum evaporating magnesium and silver on the second electron transport layer 8 to obtain a cathode 9 with the thickness of 15nm, wherein the mass ratio of Mg to Ag is 9:1;
9) The high refractive index hole-type material CPL-1 was vacuum deposited on the cathode 9 to a thickness of 100nm, and used as a cathode coating layer (capping layer or CPL) 10.
The compounds and structures of the compounds involved in this example are shown below:
device example 2
In comparison with the device example 1, the manufacturing process of the device example 2 is the same as the materials and the manufacturing steps of the layers except that HT1 in the first hole transport layer 3 and the second hole transport layer 4 is replaced with HT2.
Device example 3
In comparison with [ device example 1], the manufacturing process of [ device example 2] was the same as the materials and the manufacturing steps of the layers except that HT1 in the first hole transport layer 3 and the second hole transport layer 4 was replaced with HT3.
Device example 4
In comparison with the device example 1, the manufacturing process of the device example 2 is the same as the materials and the manufacturing steps of the layers except that HT1 in the first hole transport layer 3 and the second hole transport layer 4 is replaced with HT8.
Device example 5
In comparison with the device example 1, the manufacturing process of the device example 2 is the same as the materials and the manufacturing steps of the layers except that HT1 in the first hole transport layer 3 and the second hole transport layer 4 is replaced with HT16.
Device example 6
In comparison with the device example 1, the manufacturing process of the device example 2 is the same as the materials and the manufacturing steps of the layers except that HT1 in the first hole transport layer 3 and the second hole transport layer 4 is replaced with HT21.
Device example 7
In comparison with [ device example 1], the manufacturing process of [ device example 2] was the same as the materials and the manufacturing steps of each layer except that HT1 in the first hole transport layer 3 and the second hole transport layer 4 was replaced with HT45.
Device example 8
In comparison with [ device example 1], the manufacturing process of [ device example 2] was the same as the materials and the manufacturing steps of the layers except that HT1 in the first hole transport layer 3 and the second hole transport layer 4 was replaced with HT49.
Device example 9
In comparison with the device example 1, the manufacturing process of the device example 2 was the same as the materials and the manufacturing steps of the layers except that HT1 in the first hole transport layer 3 and the second hole transport layer 4 was replaced with HT61.
Device comparative example 1
In comparison with the device example 1, the manufacturing process of the device comparative example 1 was the same as the materials and the manufacturing steps of the layers except that HT1 in the first hole transport layer 3 and the second hole transport layer 4 was replaced with HT-ref.
HT-Ref.
TABLE 2 results of device luminescence property test
As can be seen from table 2, the device examples corresponding to the inventive materials HT1, HT2, HT3, HT8, HT16, HT21, HT45, HT49 and HT61 have lower driving voltages, greater device efficiencies and longer device lifetimes than the device comparative examples. This is due to the fact that the material of the invention has a shallower HOMO energy level value and a suitable LUMO energy level value, which reduces the injection energy barrier of holes, and thus reduces the device driving voltage; the effective injection and transmission of the holes lead to the migration balance of the holes and electrons in the device, improve the recombination probability of the electrons and the holes, reduce the generation of non-radiative heat, and improve the luminous efficiency and the service life of the device.
In table 2, the hole transport material used in device comparative example 1 was HT-ref, and the device comparative example exhibited a higher device driving voltage, which may be related to the fact that the fused benzene ring on the benzoxanthene group was only attached to a single diarylamine group. A single diarylamine group may result in insufficient electron-donating ability of the molecule to support efficient injection of holes, thereby increasing the device drive voltage.
Yet another aspect of the present invention also provides a display device comprising an organic light emitting display panel as described above.
In the present invention, the organic light emitting device may be an OLED, which may be used in an organic light emitting display device, wherein the organic light emitting display device may be a mobile phone display screen, a computer display screen, a television display screen, a smart watch display screen, a smart car display panel, a VR or AR helmet display screen, display screens of various smart devices, or the like. Fig. 3 is a schematic diagram of a display device according to an embodiment of the present invention. In fig. 3, 20 denotes a mobile phone display panel, and 30 denotes a display device.
The foregoing description of the preferred embodiments of the present invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, alternatives, and alternatives falling within the spirit and scope of the invention.
Claims (7)
1. A compound, characterized in that said compound is selected from the group consisting of:
2. the chemical process of claim 1A compound characterized in that the triplet energy level E of the compound T Is 2.6eV or more.
3. The compound according to claim 1, characterized in that it has a glass transition temperature T g Is above 120deg.C.
4. A display panel comprising an organic light-emitting device comprising an anode, a cathode, at least one organic compound layer between the anode and the cathode, wherein the organic compound of the organic compound layer comprises at least one of the compounds of any one of claims 1 to 3.
5. The display panel according to claim 4, wherein the organic compound layer includes a hole transport layer containing at least one of the compounds according to any one of claims 1 to 3.
6. The display panel according to claim 5, wherein the organic compound layer includes a hole injection layer containing at least one of the compounds according to any one of claims 1 to 3.
7. A display device comprising the display panel of any one of claims 4 to 6.
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| KR20190118514A (en) * | 2018-04-10 | 2019-10-18 | 주식회사 엘지화학 | Polycyclic compound and organic light emitting device comprising the same |
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| KR20190118514A (en) * | 2018-04-10 | 2019-10-18 | 주식회사 엘지화학 | Polycyclic compound and organic light emitting device comprising the same |
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