CN111233845A - Compound, display panel and display device - Google Patents
Compound, display panel and display device Download PDFInfo
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Abstract
The invention belongs to the technical field of OLED and provides a compound used as an OLED electron transport material, which has a structure shown in chemical formula 1. The molecules of the compound comprise triazine groups and anthracene rings, and also comprise dibenzothiophene or dibenzofuran groups. The anthracene ring has strong electron donating capability and has a bipolar characteristic, so that the electron mobility and the hole mobility of the material are balanced, and meanwhile, the anthracene ring has larger conjugation degree and higher mobility. The molecular structure of the compound is beneficial to the combination of holes and electrons to generate excitons, thereby improving the electron mobility of the material and improving the efficiency of the device. The invention also provides a display panel and a display device.
Description
Technical Field
The invention belongs to the technical field of OLED, and particularly relates to a compound used as an electron transport material, a display panel comprising the compound and a display device comprising the compound.
Background
The electron transport material used in conventional electroluminescent devices is Alq3, but the electron mobility ratio of Alq3 is low (approximately l0-6cm2/Vs), making the electron transport and hole transport of the device unbalanced. With the commercialization and practicability of electroluminescent devices, electronic transmission materials having higher transmission efficiency and better usability are desired. In this field, researchers have done a great deal of exploratory work.
Most of the electron transport materials currently used in the market, such as batho-phenanthroline (BPhen), Bathocuproine (BCP) and TmPyPB, can substantially meet the market demand of organic electroluminescent panels, but their glass transition temperature is low, generally less than 85 ℃, and the generated joule heat during device operation can cause molecular degradation and change of molecular structure, resulting in low panel efficiency and poor thermal stability. Meanwhile, the molecular structures have high symmetry and are easy to crystallize after a long time. Once the electron transport material is crystallized, the intermolecular charge jump mechanism is different from the normal amorphous thin film mechanism, resulting in the decrease of electron transport performance, the imbalance of electron and hole mobility of the whole device, the great decrease of exciton formation efficiency, and the concentration of exciton formation at the interface of the electron transport layer and the light emitting layer, resulting in the serious decrease of device efficiency and lifetime.
Therefore, the LED has the advantages of stable and efficient design and development, high electron mobility and high glass transition temperature, improves the luminous efficiency of the device, prolongs the service life of the device and has important practical application value.
Disclosure of Invention
In view of the above, the present invention provides a compound useful as an electron transport material, the compound having a general structure represented by [ chemical formula 1 ]:
wherein, X1、X2And X3Each independently selected from N atom or C atom, and X1、X2And X3At least one of them is an N atom;
R1and R2Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C4-C60 heteroaryl, substituted or unsubstituted C12-C60 fused aryl, and C10-C30 fused heteroaryl;
L1、L2and L3Each independently selected from the group consisting of a single bond, a substituted or unsubstituted C6-C40 arylene, and a substituted or unsubstituted C5-C40 heteroarylene; l is1、L2And L3In which at most one is a single bond, and L1、L2And L3One or two of them are selected from anthracenylene;
Ar1is [ chemical formula 2 ]]The group shown:
wherein Y is selected from O or S atoms;
R3selected from hydrogen atoms, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, and substituted or unsubstituted C10-C30 fused aryl groups;
# denotes the ligation site.
The invention provides an electron transport material containing triazine groups and anthracyclines, which has proper HOMO and LUMO values and can effectively improve electron transport capacity. The compound provided by the invention has high electron mobility, excellent thermal stability and film stability, and is beneficial to improving the luminous efficiency.
In the compounds of the present invention, L1、L2、L3At most one is a single bond and it is necessary for one L to be an anthracenylene group. The existence of large condensed ring groups such as anthracene groups in the molecules of the compound is beneficial to better overlapping of LUMO orbitals between molecules, thereby being beneficial to electron transmission.
Drawings
Figure 1 shows the chemical structure of an exemplary compound of the invention, ET 001;
FIG. 2 is a schematic structural diagram of an OLED device provided by 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.
An aspect of the present invention provides a compound useful as an electron transport material, the compound having a general structure represented by [ chemical formula 1 ]:
wherein, X1、X2And X3Each independently selected from N atom or C atom, and X1、X2And X3At least one of them is an N atom;
R1and R2Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C4-C60 heteroaryl, substituted or unsubstituted C12-C60 fused aryl, and C10-C30 fused heteroaryl;
L1、L2and L3Each independently selected from the group consisting of a single bond, a substituted or unsubstituted C6-C40 arylene, and a substituted or unsubstituted C5-C40 heteroarylene; l is1、L2And L3In which at most one is a single bond, and L1、L2And L3One or two of them being an anthracenylene group；
Ar1Is [ chemical formula 2 ]]The group shown:
wherein Y is selected from O or S atoms;
R3selected from hydrogen atoms, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, and substituted or unsubstituted C10-C30 fused aryl groups;
# denotes the ligation site.
The invention provides a triazine-containing electron transport material, which has proper HOMO and LUMO values and can effectively improve the electron transport capacity. The compound provided by the invention has high electron mobility, excellent thermal stability and film stability, and is beneficial to improving the luminous efficiency.
Further, in the compound of the present invention, L1、L2、L3At most one is a single bond and it is necessary that one L is an anthracenylene group. The existence of large condensed ring groups such as anthracene groups in the molecules of the compound is beneficial to better overlapping of LUMO orbitals between molecules, thereby being beneficial to electron transmission.
In one embodiment of the compounds of the present invention, X1、X2And X3Are all nitrogen atoms.
The electron accepting capacity, the migration capacity, the chemical stability and the thermal stability of the triazine group are relatively excellent, and the triazine group is suitable for mass production; meanwhile, the triazine group and the dopant have good coordination effect.
According to one embodiment of the compounds of the present invention, L1、L2And L3Each independently selected from any one of the groups shown below:
Z1and Z2Each independently selected from a hydrogen atom, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C12 to C20 fused aryl group, a substituted or unsubstituted C6 to C20 fused heteroaryl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 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, L1、L2And L3Each independently selected from any one of the groups shown below:
according to one embodiment of the compounds of the present invention, Ar1Any one selected from the structures shown below:
in the embodiment, the anthracene ring has strong electron donating capability, and the anthracene has a bipolar characteristic, so that the electron mobility and the hole mobility of the material are balanced, and meanwhile, the anthracene ring has a larger conjugation degree and a better mobility.
Dibenzofuran or dibenzothiophene is a stable weak electron donating group that acts to modulate the electron accepting ability of molecules, to modulate the degree of stacking between adjacent molecules, and to modulate the solubility of molecules.
According to one embodiment of the compound of the present invention, in [ chemical formula 2 ]]In, R3Is selected from one of alkyl, alkoxy, phenyl, biphenyl, naphthyl, phenanthryl, anthryl, pyridyl, pyrimidyl, pyrazinyl, triazinyl and benzimidazolyl. R3The existence of the group can increase the torsion resistance of the molecule, improve the solubility of the molecule and is beneficial to cleaning the mask after evaporation. R3The presence of (a) may also improve the conjugation plane of the molecule, thereby enhancing the electron mobility of the molecule.
According to one embodiment of the compounds of the present invention, the compound is selected from the following compounds:
according to one embodiment of the compound of the present invention, the compound has a glass transition temperature greater than or equal to 120 ℃.
The compounds of the invention can be used as electron transport materials for OLEDs. Figure 1 shows the chemical structure of an exemplary compound of the present invention, ET 001.
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 an electron transport layer and a light-emitting layer which are positioned between the anode and the cathode, wherein the material of the electron transport layer comprises one or more of the compounds disclosed by the invention.
According to the display panel of the invention, the display panel further comprises an electron injection layer, and the energy level difference between the LUMO energy level value of the material of the electron transport layer and the LUMO energy level value of the material of the light emitting layer or the electron injection layer is less than 0.2 eV; and the HOMO energy level value of the material of the electron transport layer is at least 0.3eV greater than the HOMO energy level value of the material of the electron injection layer. By defining the difference between LUMO levels of the respective materials, electron transport efficiency of a light emitting device in a display panel can be secured, thereby securing light emitting efficiency of the light emitting device.
According to the display panel of the present invention, the electron injection layer includes the compound of the present invention and a doping metal. Preferably the doping metal is selected from one or more of the metals sodium, potassium, calcium, cesium and ytterbium. The doped metal can solve the problems of over high energy barrier of an interface between an electron transport layer and a cathode and low performance of the organic light-emitting display panel in the existing organic light-emitting display panel. By doping metal in the electron injection layer, the purposes of reducing the interface energy barrier between the electron transport layer and the cathode of the organic light-emitting display panel, improving the electron injection capability and improving the performance of the organic light-emitting display panel are achieved.
According to the display panel of the present invention, the organic light emitting device further includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, or an electron injection layer.
The luminescent performance of different devices requires reasonable matching of the luminescent functional layers. Thus, different organic light emitting functional layers may be selected according to different display requirements and selected compounds.
Another aspect of the invention illustratively describes the synthesis of organic compounds ET001, ET006, ET010, ET019, ET031, ET044, and ET 048.
Example 1
Synthesis of Compound ET001
In a 250mL round bottom flask, 2- (4-chloro-phenyl) -4, 6-diphenyl-triazine (10mmol), 10-bromo-9-anthracene-boronic acid (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and a reflux reaction was carried out under a nitrogen atmosphere for 20 hours to obtainThe intermediate of (a) 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 ET 001-1.
In a 250mL round-bottom flask, intermediate ET001-1(10mmol), 4-boronic acid-dibenzofuran (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain final product ET 001.
Elemental analysis result of Compound ET001 (formula C)47H29N3O): theoretical value: c, 86.61; h, 4.48; n, 6.45; o, 2.45. Test values are: c, 86.61; h, 4.49; n, 6.43; o, 2.45. ESI-MS (M/z) (M) by LC-MS combined analysis+): the theoretical value is 651.23 and the test value is 651.75.
Example 2
Synthesis of Compound ET006
In a 250mL round bottom flask, 2- (4-chloro-naphthyl) -4, 6-diphenyl-triazine (10mmol), 10-bromo-9-anthracene-boronic acid (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, followed by washing with water and using anhydrousAfter drying over magnesium sulfate, filtration and evaporation, the crude product was purified by silica gel column chromatography to give intermediate ET 006-1.
In a 250mL round-bottom flask, intermediate ET006-1(10mmol), 2-boronic acid-dibenzofuran (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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 final product ET 006.
Elemental analysis result of Compound ET006 (formula C)51H31N3O): theoretical value: c, 87.28; h, 4.45; n, 5.99; o, 2.28. Test values are: c, 87.28; h, 4.44; n, 5.98; o, 2.28. ESI-MS (M/z) (M) by LC-MS combined analysis+): the theoretical value is 701.25 and the test value is 701.81.
Example 3
Synthesis of Compound ET010
In a 250mL round bottom flask, 2-chloro-4, 6-diphenyl-triazine (10mmol), 10- (4-bromo-phenyl) -9-anthracene-boronic acid (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate ET 010-1.
At 250mIn an L round-bottomed flask, intermediate ET010-1(10mmol), 1-boronic acid-dibenzofuran (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, 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 final product ET 010.
Elemental analysis result of Compound ET010 (formula C)47H29N3O): theoretical value: c, 86.61; h, 4.48; n, 6.45; o, 2.45. Test values are: c, 86.61; h, 4.47; n, 6.46; o, 2.45. ESI-MS (M/z) (M) by LC-MS combined analysis+): the theoretical value is 651.23 and the test value is 651.75.
Example 4
Synthesis of Compound ET019
In a 250mL round bottom flask, 2- (4-chloro-naphthyl) -4, 6-diphenyl-triazine (10mmol), 10-bromo-9-anthracene-boronic acid (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, filtration and evaporation, and the crude product was purified by silica gel column chromatography to obtain intermediate ET 019-1.
In a 250mL round-bottom flask, intermediate ET019-1(10mmol), 5-phenyl-3-boronic acid-dibenzofuran (12mmol) and Na2CO3(80mmol) were added separatelyTo toluene/EtOH (absolute ethanol)/H2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain final product ET 019.
Elemental analysis result of Compound ET019 (formula C)57H35N3O): theoretical value: c, 88.01; h, 4.53; n, 5.40; and O, 2.06. Test values are: c, 88.01; h, 4.52; n, 5.40; and O, 2.06. ESI-MS (M/z) (M) by LC-MS combined analysis+): the theoretical value is 777.28 and the test value is 777.91.
Example 5
Synthesis of Compound ET031
In a 250mL round bottom flask, 2- (4-chloro-naphthyl) -4, 6-biphenylyl-triazine (10mmol), 10-bromo-9-anthracene-boronic acid (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, filtration and evaporation, and the crude product was purified by silica gel column chromatography to obtain intermediate ET 031-1.
In a 250mL round-bottom flask, intermediate ET031-1(10mmol), 2-boronic acid-dibenzofuran (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) Adding into the above mixed solution, refluxing under nitrogen atmosphere for 20 hr to obtain intermediate, cooling to room temperature, adding into water, filtering with diatomite pad, extracting with dichloromethane, washing with water, drying with anhydrous magnesium sulfate, filtering, evaporating, and purifying with silica gel column chromatography to obtain final product ET 031.
Elemental analysis result of Compound ET031 (formula C)63H39N3O): theoretical value: c, 88.60; h, 4.60; n, 4.92; o, 1.87. Test values are: c, 88.60; h, 4.61; n, 4.92; o, 1.87. ESI-MS (M/z) (M) by LC-MS combined analysis+): the theoretical value is 853.31 and the test value is 854.00.
Example 6
Synthesis of Compound ET044
In a 250mL round bottom flask, 2- (4-chloro-naphthyl) -4, 6-diphenyl-triazine (10mmol), 10- (4-bromo-phenyl) -9-anthracene-boronic acid (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate ET 044-1.
In a 250mL round-bottom flask, intermediate ET044-1(10mmol), 1-boronic acid-dibenzofuran (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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 cooledAfter filtration through a pad of celite while extracting with dichloromethane, then washing with water and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to give the final product ET 044.
Elemental analysis result of Compound ET044 (formula C)57H35N3O): theoretical value: c, 88.01; h, 4.53; n, 5.40; and O, 2.06. Test values are: c, 88.01; h, 4.55; n, 5.39; and O, 2.06. ESI-MS (M/z) (M) by LC-MS combined analysis+): the theoretical value is 777.28 and the test value is 777.91.
Example 7
Synthesis of Compound ET048
In a 250mL round bottom flask, 2- (4-chloro-phenyl) -4, 6-diphenyl-triazine (10mmol), 10-bromo-9-anthracene-boronic acid (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate ET 048-1.
In a 250mL round-bottom flask, intermediate ET048-1(10mmol), 2-boronic acid-dibenzothiophene (12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) 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, filtered and evaporated, and then, a silica gel was usedThe crude product was purified by column chromatography to give ET048 as the final product.
Elemental analysis result of Compound ET048 (formula C)47H29N3S): theoretical value: c, 84.53; h, 4.38; n, 6.29; and S, 4.80. Test values are: c, 84.53; h, 4.38; n, 6.30; and S, 4.80. ESI-MS (M/z) (M) by LC-MS combined analysis+): the theoretical value is 667.21 and the test value is 667.57.
Device example 1 blue organic light emitting device (Compound of the present invention used as an Electron 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 9:1) and a cap layer (CPL)10, wherein the thickness of the ITO anode 2 is 15nm, the thickness of the first hole transport layer 3 is 10nm, the thickness of the second hole transport layer 4 is 95nm, the thickness of the electron blocking layer 5 is 30nm, the thickness of the light emitting layer 6 is 30nm, the thickness of the first electron transport layer 7 is 30nm, the thickness of the second electron transport layer 8 is 5nm, the thickness of the magnesium-silver electrode 9 is 15nm and the thickness of the cap layer (CPL)10 is 100 nm.
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-1: HAT-CN obtained in example 1, on the ITO anode 2 in a vacuum evaporation mode, wherein a layer with the thickness of 10nm is obtained by the mass ratio of a compound HT1 to HAT-CN being 98:2, and the layer is used as a first hole transmission layer 3;
3) vacuum evaporating a material HT-1 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 a compound BH is used as a main material, a compound BD is used as a doping material, the mass ratio of the compound BH to the compound BD is 97:3, and the thickness of the light-emitting layer 6 is 30 nm;
6) vacuum evaporation is carried out on the material ET001 of the first electron transport layer 7 on the luminescent layer 6 to obtain the first electron transport layer 7 with the thickness of 30 nm;
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: 1;
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, HT-1, Prime-1, BH, BD, ET001 and CPL-1 mentioned in the steps are respectively shown as follows:
device example 2
In comparison with device example 1, the fabrication process of device example 2 is the same for each layer except that the first electron transport layer 7 is ET 006.
Device example 3
In comparison to device example 1, the fabrication process of device example 3 was identical for each layer except that the first electron transport layer 7 was ET 010.
Device example 4
Device example 4 was fabricated using the same materials as device example 1, except that ET019 was used for the first electron transport layer 7.
Device example 5
Compared with device example 1, the manufacturing process of device example 5 is the same for each layer except that the first electron transport layer 7 is ET 031.
Device example 6
In comparison with device example 1, the fabrication process of device example 6 was identical for each layer except that the first electron transport layer 7 was ET 044.
Device example 7
In comparison with device example 1, the fabrication process of device example 7 was identical for each layer except that the first electron transport layer 7 was ET 047.
Comparative device example 1
In comparison with device example 1, the fabrication process of device comparative example 1 is the same for each layer except that the first electron transport layer 7 is the compound ET-Ref 1.
Comparative device example 2
In comparison with device example 1, the fabrication process of device comparative example 2 is the same for each layer except that the first electron transport layer 7 is the compound ET-Ref 2.
Table 1 table of test results of device examples and device comparative examples
Note: E/CIEy represents the ratio of efficiency (E) to CIEy.
As can be seen from table 1 above, device examples 1 to 7 to which the materials of the present invention were applied, ET001, ET006, ET010, ET019, ET031, ET044, and ET048 had lower driving voltage, higher device efficiency, and longer device lifetime than device comparative example 1 and device comparative example 2.
Compared with the device comparative example 1, the anthracene ring-bound dibenzofuran has the following advantages compared with the naphthalene-bound dibenzofuran: the anthracene ring has strong electron donating capacity, the anthracene has a bipolar characteristic, so that the electron mobility and the hole mobility of the material are balanced, and meanwhile, the anthracene ring has larger conjugation degree and better mobility, so that the compound has higher efficiency.
Compared with the device comparative example 2, the existence of azafluorene can enhance the electron accepting capability of the compound molecule, so that the resistance of electron injection and migration is increased, and the voltage of the device is increased. Meanwhile, dibenzofuran is more stable than azafluorene group, and thus, the device lifetime in comparative device example 2 is not longer than that of device examples 1 to 7.
The data in table 1 show that the compound structure of the present invention can better interact with dopants, and the presence of anthracyclines increases the degree of molecular conjugation, which is beneficial to increasing the mobility of electrons. Meanwhile, the existence of triazine increases the density of lone pair electrons in the material, and is beneficial to the interaction with dopants. The compound can effectively promote the balanced recombination of electrons and holes in a device, improve the luminous efficiency of the device, reduce the generation of non-radiative heat and effectively prolong the service life of the device.
Still another aspect of the present invention also provides a display device including the organic light emitting display panel as described above.
In the invention, the organic light emitting display device can be a mobile phone display screen, a computer display screen, a television display screen, an intelligent watch display screen, an intelligent automobile display panel, a VR or AR helmet display screen, display screens of various intelligent devices and the like. Fig. 3 is a schematic diagram of a display device according to an embodiment of the present invention, and an alternative display device is a smart phone 30. In fig. 3, the display device includes an organic light emitting display panel 20 provided by an embodiment of the present invention.
Although the present application has been described with reference to 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 application.
Claims (10)
1. A compound having a general structure represented by [ chemical formula 1 ]:
wherein, X1、X2And X3Each independently selected from N atom or C atom, and X1、X2And X3At least one of them is an N atom;
R1and R2Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C4-C60 heteroaryl, substituted or unsubstituted C12-C60 fused aryl, and C10-C30 fused heteroaryl;
L1、L2and L3Each independently selected from the group consisting of a single bond, a substituted or unsubstituted C6-C40 arylene, and a substituted or unsubstituted C5-C40 heteroarylene; l is1、L2And L3In which at most one is a single bond, and L1、L2And L3One or two of them are selected from anthracenylene;
Ar1is [ chemical formula 2 ]]The group shown:
wherein Y is selected from O or S atoms;
R3selected from hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, or mixtures thereofSubstituted or unsubstituted heteroaryl of C4-C30, substituted or unsubstituted fused aryl of C10-C30;
# denotes the ligation site.
2. The compound of claim 1, wherein X is1、X2And X3Are all nitrogen atoms.
3. A compound according to claim 1 or 2, wherein L is1、L2And L3Each independently selected from any one of the groups shown below:
Z1and Z2Each independently selected from a hydrogen atom, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C12 to C20 fused aryl group, a substituted or unsubstituted C6 to C20 fused heteroaryl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group;
p and q are each independently selected from 1, 2, 3;
# denotes the ligation site.
4. A compound of claim 3, wherein L is1、L2And L3Each independently selected from any one of the groups shown below:
5. the compound of claim 1, wherein Ar is Ar1Any one selected from the structures shown below:
# denotes the ligation site.
6. The compound of claim 1, wherein [ chemical formula 2 ]]In, R3Is selected from one of alkyl, alkoxy, phenyl, biphenyl, naphthyl, phenanthryl, anthryl, pyridyl, pyrimidyl, pyrazinyl, triazinyl and benzimidazolyl.
7. The compound of claim 1, wherein the compound is selected from the group consisting of:
8. the compound according to any one of claims 1 to 7, wherein the compound has a glass transition temperature greater than or equal to 120 ℃.
9. A display panel comprising an organic light emitting device, wherein the organic light emitting device comprises an anode, a cathode, an electron transport layer and a light emitting layer disposed between the anode and the cathode in an opposing relationship, wherein the material of the electron transport layer comprises one or more of the compounds of any one of claims 1 to 8.
10. A display device comprising the display panel of claim 9.
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