CN111253377B - Compound, display panel and display device - Google Patents
Compound, display panel and display device Download PDFInfo
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- CN111253377B CN111253377B CN202010131505.7A CN202010131505A CN111253377B CN 111253377 B CN111253377 B CN 111253377B CN 202010131505 A CN202010131505 A CN 202010131505A CN 111253377 B CN111253377 B CN 111253377B
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Abstract
The present invention belongs to the technical field of OLED and provides a compound used as a hole transport material and an electron blocking material, wherein the compound has a chemical formula 1]The general structure shown in [ chemical formula 1]]In, L 1 And L 2 Each independently selected from a single bond, a substituted or unsubstituted C6-C40 arylene, or a substituted or unsubstituted C4-C40 heteroarylene; ar (Ar) 1 And Ar 2 Each independently selected from [ chemical formula 2]]And [ chemical formula 3]A group represented by, and Ar 1 And Ar 2 Are different from each other. The compound contains carbazole and diarylamine structures, has good hole transport capability, and the addition of dibenzothiophene or dibenzofuran groups can effectively adjust the HOMO energy level of molecules so as to be matched with materials of other light-emitting functional layers. The invention also provides a display panel and a display device.
Description
Technical Field
The invention belongs to the technical field of OLED (organic light emitting diode), and particularly relates to a compound mainly used as a hole transport material and an electron blocking material, a display panel comprising the compound and a display device comprising the compound.
Background
The small and medium-sized OLED screens such as mobile phone consumer products and the like mostly adopt R, G and B sub-pixel display modes. In order to improve the production yield, some functional layers are designed as common layers, which can reduce the use of FMM (fine metal mask), and the hole transport layer is often a common layer, which can be a commercially available material.
There are several problems with existing hole transport material technology. Firstly, the poor solubility of the material can cause the poor cleaning effect of the evaporation mask in mass production; secondly, the mobility of the material is too slow, which can cause the integral voltage of the device to be too high; thirdly, the mobility of the material is too fast, especially the lateral mobility of the material is too fast, so that crosstalk occurs between adjacent pixels; fourthly, the LUMO energy level of the material is too deep to effectively block the electron migration which may cross the light-emitting layer; fifthly, the triplet state energy level of the material is low, and effective transmission of holes in RGB three colors cannot be realized simultaneously, so that the use number of masks is increased and the process difficulty is improved.
Therefore, there is a need to design and develop hole transport materials with better performance.
Disclosure of Invention
The present invention provides a compound having a general structure represented by [ chemical formula 1 ]:
wherein, in [ chemical formula 1]In, L 1 And L 2 Each independently selected from a single bond, a substituted or unsubstituted C6-C40 arylene, or a substituted or unsubstituted C4-C40 heteroarylene;
Ar 1 and Ar 2 Each independently selected from [ chemical formula 2]]And [ chemical formula 3]A group represented by, and Ar 1 And Ar 2 Are different from each other;
in [ chemical formula 2]]In, R 1 And R 2 Each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C12-C40 fused aryl, substituted or unsubstituted C4-C40 heteroaryl;
in [ chemical formula 3], cy represents a fused C6-C20 aromatic ring, and X is selected from an O atom or an S atom;
the hetero atoms in the heteroaryl or heteroarylene are selected from one or more of P, S, N, O, B and Si;
* Indicating the connection location.
The compound provided by the invention contains a hole transport material of fused ring oxafluorene/thiafluorene, carbazole group and diarylamine group. The compound molecules of the material have a shallow LUMO value and a proper HOMO value, so that the transmission capability of holes can be effectively improved, and the transition of electrons can be effectively blocked. The compounds of the invention also have a relatively high triplet energy level E T The organic electroluminescent material can effectively block the transmission of excitons, limit the excitons in the light-emitting layer and improve the transmission of holes. In addition, the compound provided by the invention has high hole 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 one exemplary compound of the invention HT 001;
FIG. 2 is a schematic structural diagram of an OLED device provided by an embodiment of the present invention;
fig. 3 is a schematic diagram of a display device according to an embodiment of the present invention.
Detailed Description
The present invention is further illustrated by the following examples and comparative examples, which are intended to be illustrative only and are not to be construed as limiting the invention. The technical scheme of the invention is to be modified or replaced equivalently without departing from the scope of the technical scheme of the invention, and the technical scheme of the invention is covered by the protection scope of the invention.
One aspect of the present invention provides a compound having a general structure represented by [ chemical formula 1 ]:
wherein in [ chemical formula 1]In, L 1 And L 2 Each independently selected from a single bond, a substituted or unsubstituted C6-C40 arylene, or a substituted or unsubstituted C4-C40 heteroarylene;
Ar 1 and Ar 2 Each independently selected from [ chemical formula 2]]And [ chemical formula 3]A group represented by, and Ar 1 And Ar 2 Are different from each other;
in [ chemical formula 2]]In, R 1 And R 2 Each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C12-C40 fused aryl, substituted or unsubstituted C4-C40 heteroaryl;
in [ chemical formula 3], cy represents a fused C6-C20 aromatic ring, and X is selected from an O atom or an S atom;
the hetero atoms in the heteroaryl or heteroarylene are selected from one or more of P, S, N, O, B and Si;
* Indicating the connection location.
The compound has carbazole and arylamine structures and has good hole transmission capability, and the addition of dibenzothiophene or dibenzofuran groups can effectively adjust the HOMO energy level of molecules so as to be matched with materials of other light-emitting functional layers.
According to one embodiment of the compounds of the present invention, L 1 And L 2 Selected from single bonds, ar 1 Selected from [ chemical formula 2]Group of formula (I), ar 2 Selected from [ chemical formula 3]The group shown. The molecule synthesis of this example is simple and does not increase the length of the conjugated chain of the molecule itself, and thus does not cause deterioration in the absorption of the hole transport material.
According to the inventionOne embodiment of the compound is represented by [ chemical formula 2]]In, R 1 And R 2 Selected from phenyl. [ chemical formula 2]R in the group of 1 And R 2 When the compound is selected from phenyl, the solubility of molecules is not deteriorated, so that the difficulty of cleaning a mask is not increased, and the length of a conjugated chain of the molecules is not increased, so that the absorption of a hole-transport material is not deteriorated.
According to one embodiment of the compound of the present invention, in [ chemical formula 3], cy represents a condensed benzene ring.
According to one embodiment of the compounds of the present invention, L 1 And L 2 Each independently selected from any one of the groups shown below:
Z 1 and Z 2 Each independently selected from a hydrogen atom, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 fused heteroaryl group, a substituted or unsubstituted C1-C16 alkyl group, a substituted or unsubstituted C1-C16 alkoxy group;
p and q are each independently selected from 1,2, 3;
# denotes the ligation site.
According to one embodiment of the compounds of the present invention, L 1 And L 2 Each independently selected from any one of the groups shown below:
according to one embodiment of the compound of the present invention, the compound is selected from any one of the following compounds:
according to one embodiment of the compound of the invention, the triplet level E of the compound T Is 2.6eV or more. The compound has high triplet state energy level, can effectively block the transmission of excitons, limits the excitons in the light-emitting layer and prevents the loss of the excitons, thereby improving the light-emitting efficiency of the device.
According to one embodiment of the compound of the present invention, the compound has a glass transition temperature T g Is above 120 ℃.
The invention also provides a display panel comprising an organic light-emitting device, wherein the organic light-emitting device comprises an anode and a cathode which are oppositely arranged, and a hole transport layer and a light-emitting layer which are arranged between the anode and the cathode, wherein the material of the hole transport layer comprises one or more compounds disclosed by the invention.
According to one embodiment of the display panel, the display panel further comprises an electron blocking layer between the anode and the cathode, the electron blocking layer comprising one or more 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, and the like, 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 also be selected from materials that facilitate hole injection in addition to the anode materials listed above, and combinations thereof, including known materials suitable for use 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 can also be materials that facilitate electron injection and combinations thereof, including materials known to be suitable as cathodes.
In the embodiment of the present invention, the manufacturing process of the organic light emitting device is as follows: 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 can be formed by a known film formation method such as evaporation, sputtering, spin coating, dipping, ion plating, or the like. The organic thin film layer at least comprises a hole transport layer and a light-emitting layer, and the material of the hole transport layer is the compound disclosed by the invention. The organic thin film layer can also comprise an electron blocking layer, and the material of the electron blocking layer is the compound disclosed by the invention.
Another aspect of the invention illustratively describes the synthesis of compounds HT001, HT015, HT017, HT021, HT028, and HT031.
Example 1
Synthesis of Compound HT001
In a 250ml round bottom flask 4-bromo-9H-carbazole (12 mmol), copper iodide (15 mmol), potassium tert-butoxide (65 mmol), 1, 2-diaminocyclohexane (12 mmol) and 8-chloro-benzofuronaphthalene (12 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Refluxing under atmospheric conditions for 48 hours, cooling the resulting intermediate to room temperature, adding water, filtering through a pad of celite while extracting with dichloromethane, washing with water, drying over anhydrous magnesium sulfate, filtering and evaporating, and then subjecting to silica gel column chromatographyThe crude product was purified to give intermediate HT001-1.
In a 250ml round-bottom flask, the intermediate HT001-1 (12 mmol), copper iodide (15 mmol), potassium tert-butoxide (65 mmol), 1, 2-diaminocyclohexane (12 mmol) and diphenylamine (12 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux under ambient conditions for 48 hours, the resulting intermediate was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the final product HT001.
Elemental analysis result of Compound HT001 (formula C) 40 H 26 N 2 O): theoretical value: c,87.25; h,4.76; n,5.09; o,2.91. Test values are: c,87.25; h,4.75; n,5.10; o,2.91. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value was 550.20 and the test value was 550.65.
Example 2
Synthesis of Compound HT015
In a 250ml round-bottom flask, 4-bromo-9H-carbazole (12 mmol), copper iodide (15 mmol), potassium tert-butoxide (65 mmol), 1, 2-diaminocyclohexane (12 mmol) and 6-chloro-benzothiophenaphthalene (12 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux was carried out under an atmosphere for 48 hours, and the resulting intermediate was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, followed by washing with water, and after drying with anhydrous magnesium sulfate, filtration and evaporation, the crude product was purified by silica gel column chromatography to give intermediate HT015-1.
In a 250ml round-bottom flask, the intermediate HT015-1 (12 mmol), copper iodide (15 mmol), potassium tert-butoxide (65 mmol), 1, 2-diaminocyclohexane (12 mmol) and biphenyl-4-phenylamine (12 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Refluxing for 48 hours under an atmosphere, cooling the resulting intermediate to room temperature, adding waterThen, the crude product was purified by silica gel column chromatography to obtain the final product HT015 after filtration through a celite pad while extracting with dichloromethane, then washing with water, and drying with anhydrous magnesium sulfate, filtration and evaporation.
Elemental analysis result of Compound HT015 (formula C) 46 H 30 N 2 S): theoretical value: c,85.95; h,4.70; n,4.36; and S,4.99. Test values are: c,85.88; h,4.71; n,4.37; and S,5.01. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 642.23 and the test value is 642.81.
Example 3
Synthesis of Compound HT017
In a 250ml round bottom flask 4-bromo-9H-carbazole (12 mmol), copper iodide (15 mmol), potassium tert-butoxide (65 mmol), 1, 2-diaminocyclohexane (12 mmol) and 6-chloro-benzofuronaphthalene (12 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux was carried out under an atmosphere for 48 hours, and the resulting intermediate was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, filtration and evaporation, and then the crude product was purified by silica gel column chromatography to obtain intermediate HT017-1.
In a 250ml round-bottom flask, the intermediate HT017-1 (12 mmol), copper iodide (15 mmol), potassium tert-butoxide (65 mmol), 1, 2-diaminocyclohexane (12 mmol) and diphenylamine (12 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux was carried out under an atmosphere for 48 hours, and the resulting intermediate was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, filtration and evaporation, and then the crude product was purified by silica gel column chromatography to obtain the final product HT017.
Elemental analysis result of Compound HT017 (formula C017) 52 H 34 N 2 O): theoretical value: c,88.86; h,4.88; n,3.99; o is,2.28. Test values: c,88.86; h,4.90; n,3.98; o,2.28. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value was 702.27 and the test value was 702.84.
Example 4
Synthesis of Compound HT021
In a 250ml round bottom flask 4-bromo-9H-carbazole (12 mmol), copper iodide (15 mmol), potassium tert-butoxide (65 mmol), 1, 2-diaminocyclohexane (12 mmol) and 7-chloro-benzofuronaphthalene (12 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux was carried out under an atmosphere for 48 hours, and the resulting intermediate was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, followed by washing with water, and after drying with anhydrous magnesium sulfate, filtration and evaporation, the crude product was purified by silica gel column chromatography to give intermediate HT021-1.
In a 250mL round-bottom flask, intermediate HT021-1 (12 mmol), (4-boronic acid-naphthyl) -diphenylamine (12 mmol) and Na 2 CO 3 (80 mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively 2 O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, then washed with water, and dried with anhydrous magnesium sulfate, and after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain the final product HT021.
Elemental analysis result of Compound HT021 (formula C) 50 H 32 N 2 O): theoretical value: c,88.73; h,4.77; n,4.14; o,2.36. Test values are: c,88.73; h,4.79; n,4.13; o,2.36. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 676.25 and the test value is 676.80.
Example 5
Synthesis of Compound HT028
In a 250ml round bottom flask 4-bromo-9H-carbazole (12 mmol), copper iodide (15 mmol), potassium tert-butoxide (65 mmol), 1, 2-diaminocyclohexane (12 mmol) and (4-chloro-phenyl) -diphenylamine (12 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux for 48 hours under ambient. The resulting intermediate was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, and after filtration and evaporation, the crude product was purified by silica gel column chromatography to give intermediate HT028-1.
In a 250mL round-bottom flask, intermediate HT028-1 (12 mmol), 6-boronic acid-benzofuronaphthalene (12 mmol) and Na 2 CO 3 (80 mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively 2 O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution. The intermediate obtained by performing the reflux reaction for 20 hours under a nitrogen atmosphere was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, and then washed with water, and dried over anhydrous magnesium sulfate, and after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain a final product HT028.
Elemental analysis result of Compound HT028 (formula C) 46 H 30 N 2 O): theoretical value: c,88.15; h,4.82; n,4.47; o,2.55. Test values are: c,88.15; h,4.81; n,4.48; o,2.55. ESI-MS (M/z) (M +) by LC Mass Spectrometry coupled analysis: the theoretical value was 626.24 and the test value was 626.74.
Example 6
Synthesis of Compound HT031
Firing in 250ml round bottomIn a vial 4-bromo-9H-carbazole (12 mmol), copper iodide (15 mmol), potassium tert-butoxide (65 mmol), 1, 2-diaminocyclohexane (12 mmol) and (4-chloro-phenyl) -bis (4-pyridyl) -amine (12 mmol) were added to dry 1, 4-dioxane (100 ml) in N 2 Reflux was carried out under an atmosphere for 48 hours, and the resulting intermediate was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, and after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate HT031-1.
In a 250mL round-bottom flask, intermediate HT031-1 (12 mmol), 6-boronic acid-benzofuronaphthalene (12 mmol) and Na 2 CO 3 (80 mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively 2 O (75/25/50, mL) 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 the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, and after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain the final product HT031.
Elemental analysis result of Compound HT031 (formula C) 44 H 28 N 4 O): theoretical value: c,84.06; h,4.49; n,8.91; o,2.54. Test values are: c,84.06; h,4.50; n,8.90; o,2.54. ESI-MS (M/z) (M +) by liquid mass spectrometry: theoretical value is 628.23, and test value is 628.72.
Table 1 below lists HOMO, LUMO and energy level difference E of compounds HT001, HT015, HT017, HT021, HT028, HT031 and comparative examples NPB, prime-1 g And triplet energy level (E) T )。
TABLE 1
As can be seen from table 1 above, compared with the comparative material NPB, the HT001, HT015, HT017, HT021, HT028, and HT031 materials of the present invention have lower HOMO levels and higher LUMO levels, which are favorable for injection and transport of holes and blocking of electrons across the light emitting layer, and confine the holes and electrons in the light emitting layer, and increase the recombination probability of the holes and electrons, the compound of the present invention has higher triplet levels, which are favorable for limiting the backflow of excitons in the light emitting layer, and effectively confine the excitons in the light emitting layer, thereby effectively reducing the generation of non-radiative energy, and increasing the light emitting efficiency and the device lifetime.
Fabrication of organic light emitting devices
Device example 1 blue organic light-emitting device (the compound of the present invention was used as a hole transport layer material)
The present embodiment provides an organic light emitting device. As shown in fig. 2, the organic light emitting device includes: the structure of the organic electroluminescent device comprises a substrate 1, an ITO anode 2, a first hole transport layer 3, a second hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a first electron transport layer 7, a second electron transport layer 8, a cathode 9 (a magnesium silver electrode, the mass ratio of magnesium to silver is 9.
The organic light-emitting device of the present invention is prepared by the following steps:
1) The glass substrate 1 was cut into a size of 50mm × 50mm × 0.7mm, ultrasonically treated in isopropanol and deionized water, respectively, for 30 minutes, and then exposed to ozone for about 10 minutes to perform cleaning; mounting the resulting glass substrate with the ITO anode 2 on a vacuum deposition apparatus;
2) Evaporating a hole buffer layer material, namely HT 001: HAT-CN obtained in example 1, on an ITO anode 2 in a vacuum evaporation mode, wherein a layer with the thickness of 10nm is obtained by using a compound HT1 and the HAT-CN with the mass ratio of 98;
3) Vacuum evaporating a material HT001 of the second hole transport layer 4 on the first hole transport layer 3 to obtain a layer with the thickness of 95nm, wherein the layer is used as the second hole transport layer 4;
4) Evaporating a material Prime-1 on the second hole transport layer 4 to obtain a layer with the thickness of 30nm, wherein the layer is used as an electron blocking layer 5;
5) Co-depositing a light-emitting layer 6 on the electron blocking layer 5, wherein BH is used as a main material, BD is used as a doping material, the mass ratio of BH to BD is 97, and the thickness of the light-emitting layer 6 is 30nm;
6) Vacuum evaporation is carried out on the material ET-1 of the first electron transport layer 7 on the luminous layer 6 to obtain the first electron transport layer 7 with the thickness of 30nm;
7) Evaporating LiF material of the second electron transport layer 8 on the first electron transport layer 7 in vacuum to obtain the second electron transport layer 8 with the thickness of 5 nm;
8) Performing vacuum evaporation 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;
9) A hole-type material CPL-1 having a high refractive index was vacuum-deposited on the cathode 9 to a thickness of 100nm, and used as a cathode cover layer (cap layer or CPL) 10.
The structural formulas of the materials HAT-CN, HT001, BH, BD, prime-1, NPB, ET-1 and CPL-1 mentioned in the steps are respectively shown as follows:
device example 2
In comparison with [ device example 1], the manufacturing process of [ device example 2] is the same for each layer of material and the manufacturing steps except that HT001 in the first hole transport layer 3 and the second hole transport layer 4 is replaced with HT015.
Device example 3
Compared with [ device example 1], the manufacturing process of [ device example 3] is the same for each layer of material and the manufacturing steps except that HT001 in the first hole transport layer 3 and the second hole transport layer 4 is replaced with HT017.
Device example 4
In comparison with [ device example 1], the manufacturing process of [ device example 4] is the same for each layer of materials and manufacturing steps except that HT001 in the first hole transport layer 3 and the second hole transport layer 4 is replaced with HT021.
Device example 5
In comparison with [ device example 1], the manufacturing process of [ device example 5] is the same for each layer material and manufacturing steps except that HT001 in the first hole transporting layer 3 and the second hole transporting layer 4 is replaced with HT028.
Device example 6
In comparison with [ device example 1], the manufacturing process of [ device example 6] is the same for each layer except that HT001 in the first hole transport layer 3 and the second hole transport layer 4 is replaced with HT031, and the materials and the manufacturing steps are the same.
Comparative device example 1
In comparison with [ device example 1], the fabrication process of [ device comparative example 1] was the same for each layer of material and fabrication steps except that HT001 in the first hole transport layer 3 and the second hole transport layer 4 was replaced with NPB.
TABLE 2 test result tables of device example and device comparative example 1
Note: E/CIEy represents the ratio of efficiency (E) to CIEy.
As can be seen from table 2, the devices using the compounds of the present invention HT001, HT015, HT017, HT021, HT028, and HT031 had lower driving voltages, higher device efficiencies, and longer device lifetimes than the comparative device examples. The material has the HOMO and LUMO energy level values which are more matched with those of adjacent layers, and can effectively inject and transmit holes, improve the recombination probability of the holes and electrons, and further effectively improve the efficiency and the service life of a device.
Fabrication of organic light emitting devices
Device example 7 blue organic light-emitting device (Compound of the present invention used as a Material for an Electron blocking layer)
The present embodiment provides an organic light emitting device. The organic light emitting device of this example was the same in structure as device example 1 except for the materials in the respective functional layers. As shown in fig. 2, the organic light emitting device includes: the structure of the organic electroluminescent device comprises a substrate 1, an ITO anode 2, a first hole transport layer 3, a second hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a first electron transport layer 7, a second electron transport layer 8, a cathode 9 (a magnesium silver electrode, the mass ratio of magnesium to silver is 9.
The organic light-emitting device of the present invention is prepared by the following steps:
1) The glass substrate 1 was cut into a size of 50mm × 50mm × 0.7mm, ultrasonically treated in isopropanol and deionized water, respectively, for 30 minutes, and then exposed to ozone for about 10 minutes to perform cleaning; mounting the resulting glass substrate with the ITO anode 2 on a vacuum deposition apparatus;
2) On the ITO anode 2, a hole buffer layer material NPB is evaporated in a vacuum evaporation mode: HAT-CN, resulting in a layer with a thickness of 10nm as the first hole transport layer 3;
3) Vacuum evaporating a material NPB of the second hole transport layer 4 on the first hole transport layer 3 to obtain a layer with the thickness of 95nm, wherein the layer is used as the second hole transport layer 4;
4) The material HT001 obtained in example 1 was vapor-deposited on the hole transport layer 4 to obtain a layer having a thickness of 90nm, which served as the electron blocking layer 5;
5) Co-depositing a light-emitting layer 6 on the electron blocking layer 5, wherein BH is used as a main material, BD is used as a doping material, the mass ratio of BH to BD is 97, and the thickness of the light-emitting layer 6 is 30nm;
6) Vacuum evaporation is carried out on the material ET-1 of the first electron transport layer 7 on the luminous layer 6 to obtain the first electron transport layer 7 with the thickness of 30nm;
7) Evaporating LiF material of the second electron transport layer 8 on the first electron transport layer 7 in vacuum to obtain the second electron transport layer 8 with the thickness of 5 nm;
8) Performing vacuum evaporation 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;
9) A hole-type material CPL-1 having a high refractive index was vacuum-deposited on the cathode 9 to a thickness of 100nm, and used as a cathode cover layer 10 (cap layer or CPL).
The structural formulas of the materials HAT-CN, NPB, HT001, BH, BD, ET-1 and CPL-1 mentioned in the steps are respectively shown as follows:
device example 8
In comparison with [ device example 7], the manufacturing process of [ device example 8] is the same for each layer of material and the manufacturing steps except that HT001 in the electron blocking layer 5 is replaced with HT015.
Device example 9
Compared with [ device example 7], the manufacturing process of [ device example 9] is the same for each layer of material and the manufacturing steps except that HT001 in the electron blocking layer 5 is replaced with HT017.
Device example 10
In comparison with [ device example 7], the fabrication process of [ device example 10] is the same for each layer of material and fabrication steps except that HT001 in the electron blocking layer 5 is replaced with HT021.
Device example 11
In comparison with [ device example 7], the fabrication process of [ device example 11] was the same for each layer of material and fabrication steps except that HT001 in the electron blocking layer 5 was replaced with HT028.
Device example 12
In comparison with [ device example 7], the manufacturing process of [ device example 12] is the same for each layer of material and the manufacturing steps except that HT001 in the electron blocking layer 5 is replaced with HT031.
Comparative device example 2
In comparison with [ device example 7], the fabrication process of [ device comparative example 2] was the same for each layer of material and fabrication steps except that HT001 in the electron blocking layer 5 was replaced with Prime-1.
TABLE 3 test result tables of device example and device comparative example 2
As can be seen from table 3, the devices using the compounds of the present invention HT001, HT015, HT017, HT021, HT028, and HT031 had lower driving voltages, higher device efficiencies, and longer device lifetimes than the device comparative examples. This is due to the fact that the material of the present invention has a more matched HOMO to adjacent layers, and a higher LUMO energy level, which effectively blocks electrons from passing through the light emitting layer, confining the electrons within the light emitting layer and recombining with holes. The material of the invention has higher triplet state energy level, can effectively limit exciton reflux in the luminescent layer, limit excitons in the luminescent layer, improve the utilization rate of the excitons, effectively reduce the generation of non-radiative energy, and thus effectively improve the efficiency and the service life of the device.
Yet another aspect of the present invention also provides a display device comprising the 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 display screen of a mobile phone, a display screen of a computer, a display screen of a television, a display screen of a smart watch, a display panel of a smart car, a display screen of a VR or AR helmet, a display screen of various smart devices, and 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 display panel of a cellular phone, and 30 denotes a display device.
Although the present application has been described with reference to the preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the present application.
Claims (7)
1. A compound selected from any one of the following compounds:
2. a compound selected from any one of the following compounds:
3. compound according to claim 1 or 2, characterized in that the triplet energy level E of the compound T Is 2.6eV or more.
4. Compound according to claim 1 or 2, characterized in that it has a glass transition temperature T g Is above 120 ℃.
5. A display panel comprising an organic light emitting device, wherein the organic light emitting device comprises an anode, a cathode disposed opposite to each other, a hole transport layer and a light emitting layer disposed between the anode and the cathode, wherein a material of the hole transport layer comprises one or more compounds according to any one of claims 1 to 4.
6. The display panel of claim 5, further comprising an electron blocking layer between the anode and the cathode, the electron blocking layer comprising one or more of the compounds of any of claims 1 to 4.
7. A display device comprising the display panel of claim 5 or 6.
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