CN114276253A - Triarylamine organic compound containing pyrene structure and application thereof - Google Patents
Triarylamine organic compound containing pyrene structure and application thereof Download PDFInfo
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- CN114276253A CN114276253A CN202011042782.7A CN202011042782A CN114276253A CN 114276253 A CN114276253 A CN 114276253A CN 202011042782 A CN202011042782 A CN 202011042782A CN 114276253 A CN114276253 A CN 114276253A
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Abstract
The invention discloses a triarylamine organic compound containing a pyrene structure and application thereof, belonging to the technical field of semiconductors; the structure of the triarylamine organic compound containing the pyrene structure is shown in a general formula (I); the organic compound provided by the invention has higher triplet state energy level, wider band gap and higher mobility, and the device adopting the organic compound provided by the invention can effectively improve the efficiency of an OLED device and the service life of the OLED device through structure optimization.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a triarylamine organic compound containing a pyrene structure and application thereof.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device.
Disclosure of Invention
Aiming at the problems in the prior art, the applicant of the invention develops a novel triarylamine organic compound containing a pyrene structure, the triarylamine is used as a basic framework, one benzene ring connected with a nitrogen atom in the arylamine is simultaneously connected with one pyrenyl group and one aryl group, and the connection mode enables the compound of the invention to have the characteristic of high hole mobility of the traditional triarylamine organic compound containing the pyrene structure, and overcomes the defects of low T1 and narrow band gap of the traditional triarylamine organic compound containing the pyrene structure, so that a device adopting the organic compound provided by the invention can effectively reduce the voltage of an OLED device, improve the efficiency of the OLED device and prolong the service life of the OLED device through structural optimization.
The technical scheme of the invention is as follows:
the first aspect of the invention provides a triarylamine organic compound containing a pyrene structure, wherein the structure of the organic compound is shown as a general formula (I):
r represents phenyl, biphenyl or naphthyl;
ar is1、Ar2Each independently represents any one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted tetrabiphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, and substituted or unsubstituted benzophenanthryl, and Ar1、Ar2Not simultaneously represented as phenyl;
the substituent of the substituent group is optionally selected from deuterium atom, phenyl group, naphthyl group, biphenyl group, phenanthryl group or benzophenanthryl group.
In a preferred embodiment, said R represents phenyl;
preferred embodiment, said Ar1Represents a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group;
preferred embodiment, said Ar1Represented by a biphenylyl, terphenyl or quaterphenyl group;
preferred embodiment, said Ar1Represents phenyl substituted by naphthyl or phenyl substituted by phenanthryl;
preferably, the general formula (I) is represented by a structure represented by the general formula (I-1) or the general formula (I-2):
r represents phenyl, biphenyl or naphthyl;
ar is1、Ar2Each independently represents any one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted tetrabiphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, and substituted or unsubstituted benzophenanthryl, and Ar1、Ar2Not simultaneously represented as phenyl;
the substituent of the substituent group is optionally selected from deuterium atom, phenyl group, naphthyl group, biphenyl group, phenanthryl group or benzophenanthryl group.
More preferably, the specific structure of the compound is as follows:
the second aspect of the invention is to provide the application of the triarylamine organic compound containing the pyrene structure in the preparation of organic electroluminescent devices.
A third aspect of the present invention is to provide an organic electroluminescent device comprising a cathode, an anode and an organic functional layer interposed between the anode and the cathode, characterized in that the above functional layer contains the triarylamine-based organic compound having a pyrene structure.
In a fourth aspect of the present invention, there is provided an organic electroluminescent device comprising an electron blocking layer having such a feature that the electron blocking layer contains the triarylamine-based organic compound having a pyrene structure.
A fifth aspect of the present invention is to provide an organic electroluminescent device having such features, comprising a hole injection layer including a P-doped material and an organic material, a hole transport layer including the same organic material as the hole injection layer, an electron blocking layer adjacent to the light-emitting layer, a light-emitting layer, and an electron transport region.
A sixth aspect of the present invention provides an organic electroluminescent device characterized by comprising a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, and an electron transport region, wherein the electron blocking layer adjoins the light-emitting layer, the hole injection layer comprises a P-doped material and an organic material, the hole transport layer comprises the same organic material as the hole injection layer, and the electron blocking layer contains the triarylamine-based organic compound having a pyrene structure.
A seventh aspect of the present invention provides a full-color display device, which includes, in order from bottom to top, a substrate, a first electrode, an organic functional material layer, and a second electrode, the organic functional material layer including: a hole transport region over the first electrode; a light emitting layer on the hole transport region, the light emitting layer having a red light emitting layer, a green light emitting layer and a blue light emitting layer patterned in a red pixel region, a green pixel region and a blue pixel region, respectively; an electron transport region over the light emitting layer; the hole transport region sequentially comprises a hole injection layer, a hole transport layer and an electron blocking layer from bottom to top, the hole injection layer comprises a P-type doping material, the red pixel unit, the green pixel unit and the blue pixel unit share the hole injection layer and the hole transport layer and respectively comprise the electron blocking layer, and the blue pixel electron blocking layer contains the triarylamine organic compound containing the pyrene structure.
An eighth aspect of the present invention is to provide a lighting or display element having such a feature, including the organic electroluminescent device described above.
The beneficial technical effects of the invention are as follows:
according to the arylamine compound, arylamine is used as a basic framework, one benzene ring connected with nitrogen atoms in the arylamine is simultaneously connected with one pyrenyl group and one aryl group, and the connection mode enables the compound disclosed by the invention to have a wider band gap, so that electrons cannot be transferred from a light emitting layer to a hole transport layer due to the wider band gap, and the efficiency of a device is further improved.
The compound provided by the invention contains pyrenyl, and the pyrenyl has a strong pi conjugation effect, so that the compound provided by the invention has strong hole transmission capability, and the voltage of a device can be reduced at a high hole transmission rate.
However, due to the strong pi conjugation effect of pyrenyl, the pyrenyl-containing organic compound T1 is not high generally, so that the OLED device using the pyrenyl-containing organic compound has generally low efficiency and generally poor lifetime; meanwhile, since the pyrenyl is a large rigid group, the pyrenyl-containing molecules are easier to accumulate in a pi-pi mode, so that the intermolecular distance is small, the intermolecular force is large, and the vapor deposition temperature of the molecules is high during vapor deposition. Compared with the compounds in JP2011084717A and JP1994240245A, the bridging group between the pyrenyl and the diarylamine group of the compound provided by the invention not only pulls open the distance between the pyrenyl and the diarylamine group, but also improves the T1 of the molecule, thereby improving the efficiency and the service life of the organic electroluminescent device; and the distance between molecules is enlarged, and the evaporation temperature of the molecules is reduced.
The compound of the invention ensures that the distribution of electrons and holes in the luminescent layer is more balanced, and under the proper HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; can effectively improve the exciton utilization rate, reduce the efficiency roll-off of the device under high current density, reduce the voltage of the device, improve the current efficiency of the device and prolong the service life of the device. The compound has good application effect in OLED luminescent devices and good industrialization prospect.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
in the figure: 1 is a substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is hole transmission, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is an electron transmission or hole blocking layer, 8 is an electron injection layer, 9 is a cathode reflection electrode layer, and 10 is a CPL layer.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1: synthesis of target Compound
0.06mol of the raw material B was charged in a 500ml three-necked flask under a nitrogen atmosphere, and a mixed solvent (300ml of toluene, 90ml of H) was added2O) dissolving the raw materials, introducing nitrogen, stirring for 1 hour, and slowly adding 0.05mol of the raw material A and 0.1mol of the K2CO3、0.005mol Pd(PPh3)4Heating to 90 deg.C, and reactingThe reaction was observed by Thin Layer Chromatography (TLC) for 8 hours until the reaction was complete. And naturally cooling to room temperature, adding water into the reaction system for extraction, separating liquid, and performing reduced pressure rotary evaporation on the organic phase until no fraction is obtained. The resulting material was purified by silica gel column to give intermediate N.
To a 500ml three-necked flask, 0.06mol of intermediate N was added under a nitrogen atmosphere, and a mixed solvent (300ml of toluene, 90ml of H) was added2O) dissolving the raw materials, introducing nitrogen, stirring for 1 hour, and then slowly adding 0.05mol of raw material C and 0.1mol of K2CO3、0.005mol Pd(PPh3)4The reaction was heated to 90 ℃ for 8 hours, and the reaction was observed by Thin Layer Chromatography (TLC) until the reaction was complete. And naturally cooling to room temperature, adding water into the reaction system for extraction, separating liquid, and performing reduced pressure rotary evaporation on the organic phase until no fraction is obtained. The resulting material was purified by silica gel column to give intermediate M.
Adding 0.01mol of intermediate M, 0.012mol of raw material D and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5X 10-5mol Pd2(dba)3，5×10-5Heating the tri-tert-butylphosphine mol and sodium tert-butoxide 0.03mol to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to show that no chloride remains and the reaction is complete; naturally cooling to room temperature, filtering, rotatably steaming the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain the target product.
The following compounds (all raw materials were purchased from midrange energy saving wang ltd) were prepared in the same manner as in example 1, and the synthetic raw materials are shown in tables 1 and 2 below;
TABLE 1
TABLE 2
The compound of the invention is used in a light-emitting device and can be used as an electron blocking layer material. The compounds prepared in the above examples of the present invention were tested for thermal performance, T1 energy level, and HOMO energy level, respectively, and the test results are shown in table 3:
TABLE 3
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the triplet energy level T1 was measured by Fluorolog-3 series fluorescence spectrometer from Horiba under the conditions of 2X 10-5A toluene solution of mol/L; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy testing system (IPS3), which is an atmospheric environment; eg was tested by means of a two-beam UV-Vis spectrophotometer (model: TU-1901).
The data in the table show that the organic compound has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the light-emitting layer has a high T1 energy level, so that the energy loss of the light-emitting layer can be blocked, and the light-emitting efficiency and the service life of the device are improved; the wide band gap (Eg) can effectively prevent electrons from being transferred to the hole transport region, so that the luminous efficiency of the device is improved; a suitable HOMO energy level may solve the problem of carrier injection. Therefore, the triarylamine organic compound containing the pyrene structure can effectively improve the luminous efficiency and prolong the service life of the device after being applied to the electron blocking layer of the OLED device.
The effect of the synthesized OLED material of the present invention in the application of the device is detailed below by device examples 1-37 and device comparative examples 1-3. Compared with the device example 1, the device examples 2 to 37 and the device comparative examples 1 to 3 of the invention have the same manufacturing process, adopt the same substrate material and electrode material, keep the film thickness of the electrode material consistent, and are different from the difference that the material of the electron barrier layer in the device is replaced. The structural composition of the devices obtained in the respective examples is shown in table 4, and the results of the performance tests of the devices obtained in the respective examples are shown in table 5.
Device example 1
Substrate layer 1/anode layer 2(ITO (15nm)/Ag (150nm)/ITO (15 nm))/hole injection layer 3 (HT-1: P-1, 3% 10 nm)/hole transport layer 4(HT-1, thickness 120 nm)/electron blocking layer 5 (compound 2, thickness 10 nm)/light-emitting layer 6(BH-1 and BD-1 doped at a weight ratio of 97:3, thickness 20 nm)/hole blocking/electron transport layer 7(ET-1 and Liq doped at a weight ratio of 1:1, thickness 30 nm)/electron injection layer 8(LiF, thickness 1 nm)/cathode layer 9(Mg and Ag doped at a weight ratio of 1:9, thickness 16nm)/CPL layer 10 (compound CP-1, thickness 70 nm).
The preparation process comprises the following steps:
as shown in fig. 1, the anode layer 2(ITO (15nm)/Ag (150nm)/ITO (15nm)) is washed, i.e., sequentially washed with alkali, washed with pure water, dried, and then washed with ultraviolet rays and ozone to remove organic residues on the surface of the anode layer 1. HT-1 and P-1 having a film thickness of 10nm were deposited on the anode layer 2 after the above washing as the hole injection layer 3 by a vacuum deposition apparatus, and the mass ratio of HT-1 to P-1 was 97: 3. HT-1 was then evaporated to a thickness of 120nm as the hole transport layer 4. Followed by evaporation of compound 2 as electron blocking layer 5 to a thickness of 10 nm. After the evaporation of the electron blocking material is finished, the light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the OLED light emitting device comprises that BH-1 used by the OLED light emitting layer 6 is used as a main material, BD-1 is used as a doping material, the doping proportion of the doping material is 3% by weight, and the thickness of the light emitting layer is 20 nm. After the light-emitting layer 6, ET-1 and Liq are continuously evaporated, wherein the mass ratio of ET-1 to Liq is 1: 1. The vacuum evaporation film thickness of the material was 30nm, and this layer was a hole-blocking/electron-transporting layer 7. On the hole-blocking/electron-transporting layer 7, a LiF layer having a film thickness of 1nm was formed by a vacuum evaporation apparatus, and this layer was an electron-injecting layer 8. On the electron injection layer 8, a vacuum deposition apparatus was used to produce a 16 nm-thick Mg: the Ag electrode layer has a Mg/Ag mass ratio of 1:9, and is used as the cathode layer 9. On the cathode layer 9, 70nm of CP-1 was vacuum-deposited as a CPL layer 10.
Device examples 2-37: the process is carried out according to the device embodiment 1, except that the material of the electron blocking layer 5 is replaced, the specific device structure is shown in table 4, and the device performance test is shown in table 5;
comparative device examples 1 to 3 were carried out in the same manner as in example 1 except that the electron blocking layer 5 was made of EB-1, EB-2, EB-3;
the structural formula of the material involved in the preparation process is as follows:
TABLE 4
The inspection data of the obtained electroluminescent device are shown in Table 5.
TABLE 5
Note: voltage, current efficiency and color coordinates were measured using an IVL (Current-Voltage-Brightness) test System (Fushda scientific instruments, Suzhou) at a current density of 10mA/cm2(ii) a The life test system is an EAS-62C type OLED device life tester of Japan System research company; LT95 refers to the time it takes for the device brightness to decay to 95% at a particular brightness.
From the results in table 5, it can be seen that the triarylamine organic compound containing pyrene structure prepared by the invention can be applied to the fabrication of OLED luminescent devices, and compared with device comparative examples, the efficiency and the service life of the organic compound are greatly improved compared with those of the known OLED materials.
In summary, the present invention is only a preferred embodiment, and not intended to limit the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A triarylamine organic compound containing a pyrene structure is characterized in that the structure of the organic compound is shown as a general formula (I):
r represents phenyl, biphenyl or naphthyl;
ar is1、Ar2Each independently represents any one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted tetrabiphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, and substituted or unsubstituted benzophenanthryl, and Ar1、Ar2Not simultaneously represented as phenyl;
the substituent of the substituent group is optionally selected from deuterium atom, phenyl group, naphthyl group, biphenyl group, phenanthryl group or benzophenanthryl group.
2. An organic compound according to claim 1, wherein R represents a phenyl group.
3. The organic compound of claim 1, wherein Ar is Ar1Represented by substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl.
4. The organic compound of claim 1, wherein Ar is Ar1Represented as a biphenylyl, terphenyl or quaterphenyl group.
5. The organic compound of claim 1, wherein Ar is Ar1Represented by phenyl substituted by naphthyl or phenyl substituted by phenanthryl.
6. The organic compound according to claim 1, wherein the general formula (I) is represented by a structure represented by general formula (I-1) or general formula (I-2):
r represents phenyl, biphenyl or naphthyl;
ar is1、Ar2Respectively independent representationIs any one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted tetrabiphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted benzophenanthryl, and Ar1、Ar2Not simultaneously represented as phenyl;
the substituent of the substituent group is optionally selected from deuterium atom, phenyl group, naphthyl group, biphenyl group, phenanthryl group or benzophenanthryl group.
7. The organic compound of claim 1, wherein the specific structure of the compound is any one of the following structures:
8. an organic electroluminescent device comprising a cathode, an anode and an organic functional layer, wherein the organic functional layer is located between the anode and the cathode, and is characterized in that the organic functional layer contains the triarylamine organic compound containing a pyrene structure according to any one of claims 1 to 7.
9. The organic electroluminescent device according to claim 8, wherein the organic functional layer comprises an electron blocking layer, and the electron blocking layer contains the triarylamine-based organic compound having a pyrene structure according to any one of claims 1 to 7.
10. A lighting or display element comprising the organic electroluminescent device according to any one of claims 8 to 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117209422A (en) * | 2023-11-07 | 2023-12-12 | 烟台丰蓬液晶材料有限公司 | Fluorine-containing ortho-substituted triarylamine compound and organic electroluminescent device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117209422A (en) * | 2023-11-07 | 2023-12-12 | 烟台丰蓬液晶材料有限公司 | Fluorine-containing ortho-substituted triarylamine compound and organic electroluminescent device |
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