CN112409259B - Thermal activation delayed fluorescence micromolecule material, polymer material, organic electroluminescent device and preparation method - Google Patents

Thermal activation delayed fluorescence micromolecule material, polymer material, organic electroluminescent device and preparation method Download PDF

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CN112409259B
CN112409259B CN202011090650.1A CN202011090650A CN112409259B CN 112409259 B CN112409259 B CN 112409259B CN 202011090650 A CN202011090650 A CN 202011090650A CN 112409259 B CN112409259 B CN 112409259B
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delayed fluorescence
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葛子义
赵梦雨
张家森
魏强
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention relates to a thermal activation delayed fluorescence micromolecule, a polymer, an organic electroluminescent device and a preparation method thereof, wherein the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as a formula (1)
Figure DDA0002721926770000011
Wherein R is1Including alkyl groups. The thermal activation delayed fluorescence micromolecule material and the end group of the polymer are further selected from alkyl, so that the polymer has good solubility, and can be placed in a device in a solution form to play a role, and the defects of high requirement on vacuum degree, complex operation, high cost and the like of an evaporation process are overcome. Meanwhile, the terminal group of the thermally activated delayed fluorescence micromolecule material is alkyl, so that the energy level difference between the lowest singlet excitation state and the lowest triplet excitation state of the terminal group is obviously reduced, the maximum external quantum efficiency is obviously improved, and the terminal group has the advantages of better separation of the Lowest Unoccupied Molecular Orbital (LUMO) and the Highest Occupied Molecular Orbital (HOMO), good solvent color change effect and stability and the like.

Description

Thermal activation delayed fluorescence micromolecule material, polymer material, organic electroluminescent device and preparation method
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a thermal activation delayed fluorescence micromolecule material, a polymer material, an organic electroluminescent device and a preparation method.
Background
The Thermal Activation Delayed Fluorescence (TADF) material not only can make the exciton utilization rate reach 100%, but also can reduce the triplet exciton concentration, thereby inhibiting the device efficiency roll-off, so the thermal activation delayed fluorescence material becomes an important research direction in the Organic Light Emitting Diode (OLED) manufacturing field.
The traditional thermal activation delayed fluorescent material comprises benzophenone as an acceptor unit and acridine as a donor unit, but the end group of the thermal activation delayed fluorescent material is selected from a benzene ring-containing substituent group, so that the solubility is poor, and a device can be processed only in an evaporation mode, so that the requirement on vacuum degree is high, the operation is complicated, the cost is high, meanwhile, the energy level difference between a singlet state and a triplet state is still large, and the maximum external quantum efficiency, the stability and the like are also required to be improved.
Disclosure of Invention
In view of the above, it is necessary to provide a thermally activated delayed fluorescence small molecule material, a polymer material, an organic electroluminescent device and a method for manufacturing the same.
The invention provides a thermal activation delayed fluorescence micromolecule material, which has a structural formula shown in formula (1):
Figure BDA0002721926750000021
wherein R is1Selected from alkyl groups.
The thermal activation delayed fluorescence micromolecule material takes benzophenone with electron withdrawing property and a larger torsion angle as an acceptor unit and acridine with stronger electron donating capability as a donor unit, can well realize the thermal activation delayed fluorescence effect, and both the benzophenone and the acridine are rigid structures, so that the thermal activation delayed fluorescence micromolecule material has better stability. The end group of the thermal activation delayed fluorescence micromolecule material is further selected from alkyl, so that the thermal activation delayed fluorescence micromolecule material has good solubility, and therefore, the thermal activation delayed fluorescence micromolecule material can be processed and manufactured into an organic electroluminescent device through a solution method, and the defects of high requirement on vacuum degree, complex operation, high cost and the like of an evaporation process are overcome. Meanwhile, the terminal group of the thermally activated delayed fluorescence micromolecule material is alkyl, so that the energy level difference between the lowest singlet excitation state and the lowest triplet excitation state of the terminal group is obviously reduced, the maximum external quantum efficiency is obviously improved, and the terminal group has the advantages of better separation of the Lowest Unoccupied Molecular Orbital (LUMO) and the Highest Occupied Molecular Orbital (HOMO), good solvent color change effect and stability and the like.
At itIn one embodiment, the alkyl group comprises C4H9、C5H11、C6H13、C7H15、C8H17、C9H19、C10H21、C11H23、C12H25、C13H27Any one of the above.
The invention also provides a thermal activation delayed fluorescence polymer material, and the structural formula of the thermal activation delayed fluorescence polymer material is shown as the formula (2):
Figure BDA0002721926750000031
wherein R is2Represents a capping group.
The thermally activated delayed fluorescence polymer material is formed by polymerizing n monomers, wherein the monomers take benzophenone with electron-withdrawing property and a larger torsion angle as an acceptor unit and acridine with stronger electron-donating capability as a donor unit, so that the thermally activated delayed fluorescence effect can be well realized, and the benzophenone with electron-withdrawing property and the acridine with stronger electron-donating capability are both rigid structures, so that the thermally activated delayed fluorescence polymer material has better stability. The end group of the monomer is further selected from alkyl, so that the thermal activation delayed fluorescence polymer material has good solubility, and therefore, the organic electroluminescent device can be processed and manufactured by a solution method, and the defects of high requirement on vacuum degree, complex operation, high cost and the like of an evaporation process are overcome. Meanwhile, the end group of the monomer is alkyl, so that the energy level difference between the lowest singlet excitation state and the lowest triplet excitation state of the thermally-activated delayed fluorescent polymer material is obviously reduced, the maximum external quantum efficiency is obviously improved, and the thermally-activated delayed fluorescent polymer material has the advantages of better separation of the Lowest Unoccupied Molecular Orbital (LUMO) and the Highest Occupied Molecular Orbital (HOMO), good solvent discoloration effect, good stability and the like.
In one embodiment, R2Including any one of N-hexyl carbazolyl, phenylethynyl styryl and phenyl.
In one embodiment, the structural formula of the thermally activated delayed fluorescence polymer material is shown as formula (3):
Figure BDA0002721926750000041
the invention also provides an organic electroluminescent device, which comprises a cathode layer, an electron injection layer, an electron transport layer, a hole blocking layer, a light-emitting layer, a hole injection layer and an anode layer which are sequentially stacked, wherein the light-emitting layer comprises the thermal activation delayed fluorescence micromolecule material or the thermal activation delayed fluorescence polymer material.
The luminescent layer of the organic electroluminescent device comprises the thermal activation delayed fluorescence small molecular material or the thermal activation delayed fluorescence polymer material, so that the organic electroluminescent device has good stability, higher luminescent intensity and external quantum efficiency.
The invention also provides a preparation method of the luminescent layer in the organic electroluminescent device, which comprises the following steps:
preparing a hole injection layer, a luminescent layer, a hole barrier layer, an electron transport layer, an electron injection layer and a cathode layer on the anode layer in sequence;
the preparation of the light-emitting layer comprises mixing a light-emitting layer main body material, an exciton blocking layer material, a thermal activation delayed fluorescence micromolecule material or a thermal activation delayed fluorescence polymer material and an organic solvent to obtain an intermediate; and
and carrying out spin coating on the intermediate and then carrying out annealing treatment to obtain the light-emitting layer.
In one embodiment, the annealing treatment comprises heating the intermediate at a temperature of 25 ℃ to 150 ℃ for a time of 0min to 60 min.
In one embodiment, the mass ratio of the host material of the light emitting layer, the exciton blocking layer material, the thermal activation delayed fluorescence micromolecule or the thermal activation delayed fluorescence polymer to the organic solvent is 60:40:30-40:20: 10.
In one embodiment, the organic solvent comprises at least one of tetrahydrofuran, toluene, dichloromethane, chlorobenzene, and chloroform.
Drawings
FIG. 1 is a plot of M1, P1 highest occupied molecular orbital and lowest unoccupied molecular orbital;
FIG. 2 is a thermogravimetric plot of M1, P1;
FIG. 3 shows the UV-VIS absorption spectra of M1 and P1 in solution and thin film;
FIG. 4 shows fluorescence spectra of M1 and P1 in a solvent state and a thin film state;
FIG. 5 is a graph of the fluorescence spectra of M1 in different solvents;
FIG. 6 is a fluorescence spectrum of P1 in different solvents;
FIG. 7 is a fluorescence/phosphorescence plot of M1;
FIG. 8 is a fluorescence/phosphorescence plot for P1;
fig. 9 is a diagram of an organic light-emitting electroluminescent device of application example 1 of the present invention;
fig. 10 is a diagram of an organic light-emitting electroluminescent device of application example 2 of the present invention;
FIG. 11 is a graph showing electroluminescence spectra of an organic light emitting electroluminescent device of application example 1 and an organic light emitting electroluminescent device of application example 2;
fig. 12 is a current density-voltage curve of the organic light emitting electroluminescent device of application example 1 and the organic light emitting electroluminescent device of application example 2;
fig. 13 is a graph of luminous intensity versus voltage for the organic light emitting electroluminescent device of application example 1 and the organic light emitting electroluminescent device of application example 2;
fig. 14 is a current density-external quantum efficiency curve of the organic light emitting electroluminescent device of application example 1 and the organic light emitting electroluminescent device of application example 2.
In the figure: 1. an anode layer; 2. a hole injection layer; 3. a light emitting layer; 301. a light emitting layer host; 302. thermally activated delayed fluorescence material; 303. an exciton blocking layer; 4. a hole blocking layer; 5. an electron transport layer; 6. an electron injection layer; 7. and a cathode layer.
Detailed Description
The thermal activation delayed fluorescence small molecule material, the polymer material, the organic electroluminescent device and the preparation method provided by the invention are further explained below.
The invention provides a thermal activation delayed fluorescence micromolecule material, which has a structural formula shown in a formula (1):
Figure BDA0002721926750000061
wherein R is1Selected from alkyl groups.
The thermal activation delayed fluorescence micromolecule material takes benzophenone with electron withdrawing property and a larger torsion angle as an acceptor unit and acridine with stronger electron donating capability as a donor unit, can well realize the thermal activation delayed fluorescence effect, and both the benzophenone and the acridine are rigid structures, so that the thermal activation delayed fluorescence micromolecule material has better stability. The end group of the thermal activation delayed fluorescence micromolecule material is further selected from alkyl, so that the thermal activation delayed fluorescence micromolecule material has good solubility, and therefore, the thermal activation delayed fluorescence micromolecule material can be processed and manufactured into an organic electroluminescent device through a solution method, and the defects of high requirement on vacuum degree, complex operation, high cost and the like of an evaporation process are overcome. Meanwhile, the terminal group of the thermally activated delayed fluorescence micromolecule material is alkyl, so that the energy level difference between the lowest singlet excitation state and the lowest triplet excitation state of the terminal group is obviously reduced, the maximum external quantum efficiency is obviously improved, and the terminal group has the advantages of better separation of the Lowest Unoccupied Molecular Orbital (LUMO) and the Highest Occupied Molecular Orbital (HOMO), good solvent color change effect and stability and the like.
If the number of carbon atoms of the alkyl group is too small, the solubility of the thermally activated delayed fluorescence small molecular material is poor, and if the number of carbon atoms of the alkyl group is too large, the synthesis cost increases, and the thermally activated delayed fluorescence effect of the thermally activated delayed fluorescence small molecular material is insignificant, and therefore, the alkyl group preferably includes C4H9、C5H11、C6H13、C7H15、C8H17、C9H19、C10H21、C11H23、C12H25、C13H27Any of the above, more preferably C12H25。
When R is1Is C4H9When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (4):
Figure BDA0002721926750000071
when R is1Is C5H11When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (5):
Figure BDA0002721926750000072
when R is1Is C6H13When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (6):
Figure BDA0002721926750000081
when R is1Is C7H15When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (7):
Figure BDA0002721926750000082
when R is1Is C8H17When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (8):
Figure BDA0002721926750000091
when R is1Is C9H19When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (9):
Figure BDA0002721926750000092
when R is1Is C10H21When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (10):
Figure BDA0002721926750000093
when R is1Is C11H23When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (11):
Figure BDA0002721926750000101
when R is1Is C12H25When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (12):
Figure BDA0002721926750000102
when R is1Is C13H27When the material is used, the structural formula of the thermal activation delayed fluorescence micromolecule material is shown as the formula (13):
Figure BDA0002721926750000103
the invention also provides a thermal activation delayed fluorescence polymer material, and the structural formula of the thermal activation delayed fluorescence polymer material is shown as the formula (2):
Figure BDA0002721926750000111
wherein R is2Represents a capping group.
The thermally activated delayed fluorescence polymer material is formed by polymerizing n monomers, wherein the monomers take benzophenone with electron-withdrawing property and a larger torsion angle as an acceptor unit and acridine with stronger electron-donating capability as a donor unit, so that the thermally activated delayed fluorescence effect can be well realized, and the benzophenone with electron-withdrawing property and the acridine with stronger electron-donating capability are both rigid structures, so that the thermally activated delayed fluorescence polymer material has better stability. The end group of the monomer further selects alkyl, so that the thermal activation delayed fluorescence polymer material has good solubility, and can be processed and manufactured into an organic electroluminescent device by a solution method, thereby avoiding the defects of high requirement of an evaporation process on vacuum degree, complex operation, high cost and the like. Meanwhile, the end group is alkyl, so that the energy level difference between the lowest singlet excitation state and the lowest triplet excitation state of the thermally-activated delayed fluorescence polymer material is obviously reduced, the maximum external quantum efficiency is obviously improved, and the thermally-activated delayed fluorescence polymer material has the advantages of better separation of the Lowest Unoccupied Molecular Orbital (LUMO) and the Highest Occupied Molecular Orbital (HOMO), good solvent color change effect and stability and the like.
Under the polymerization degree that n is 1120, the solubility of the thermal activation delayed fluorescence polymer material is better, the energy level difference between the lowest singlet excitation state and the lowest triplet excitation state is further reduced, the maximum external quantum efficiency is further improved, and the separation degree, the solvent color change effect and the stability of LUMO and HOMO are also better.
R2The fluorescent material comprises any one of N-hexyl carbazolyl, phenylethynyl styryl and phenyl so as to ensure the thermal activation delayed fluorescence effect of the thermal activation delayed fluorescence polymer material.
Preferably, the structural formula of the thermally activated delayed fluorescence polymer material is shown as formula (3):
Figure BDA0002721926750000121
the end capping groups of the thermal activation delayed fluorescence polymer material are phenyl, so that the cost is low, and compared with other end capping groups, the thermal activation delayed fluorescence effect of the thermal activation delayed fluorescence polymer material is more obvious, and the maximum external quantum efficiency of the thermal activation delayed fluorescence polymer material is ensured.
The invention also provides an organic electroluminescent device, which comprises a cathode layer, an electron injection layer, an electron transport layer, a hole blocking layer, a light-emitting layer, a hole injection layer and an anode layer which are sequentially stacked, wherein the light-emitting layer comprises the thermal activation delayed fluorescence micromolecule material or the thermal activation delayed fluorescence polymer material.
The luminescent layer of the organic electroluminescent device comprises the thermal activation delayed fluorescence micromolecule material or the thermal activation delayed fluorescence polymer material, so that the organic electroluminescent device has good stability, high luminescent intensity and high external quantum efficiency.
The invention also provides a preparation method of the luminescent layer in the organic electroluminescent device, which comprises the following steps:
preparing a hole injection layer, a luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode layer on the anode layer in sequence to obtain an organic electroluminescent device;
the preparation of the light-emitting layer comprises mixing a light-emitting layer main body material, an exciton blocking layer material, a thermal activation delayed fluorescence micromolecule material or a thermal activation delayed fluorescence polymer material and an organic solvent to obtain an intermediate; and
and carrying out spin coating on the intermediate and then carrying out annealing treatment to obtain the light-emitting layer.
The main material of the light emitting layer and the thermal activation delayed fluorescence micromolecule material or the thermal activation delayed fluorescence polymer material are matched with each other, so that the energy level difference between the lowest singlet excitation state and the lowest triplet excitation state is obviously reduced, and the light emitting efficiency of the organic electroluminescent device is improved. The exciton blocking layer material blocks the transmission of photoproduction excitons to the cathode, and ensures the luminous efficiency of the organic electroluminescent device.
The annealing treatment comprises heating the intermediate to better improve the light emitting performance of the light emitting layer, specifically, the heating temperature is 25-150 ℃, the light emitting effect of the light emitting layer is best when the heating time is 0-60 min, and further preferably, the heating temperature is 100 ℃, and the heating time is 10 min.
Specifically, in order to ensure better interaction among the light emitting layer host material, the exciton blocking layer material, the thermally activated delayed fluorescence micromolecules or the thermally activated delayed fluorescence polymer and enable electrons in a triplet excited state to cross to a singlet excited state, the mass ratio of the light emitting layer host material, the exciton blocking layer material, the thermally activated delayed fluorescence micromolecules or the thermally activated delayed fluorescence polymer is 60:40:30-40:20:10, preferably 50:30:20, the light emitting layer host material, the exciton blocking layer material, the thermally activated delayed fluorescence micromolecules or the thermally activated delayed fluorescence polymer is used as a solute, and 10mg-20mg of the solute is added into each milliliter of organic solvent.
The solubility and the color change effect of the heat-activated delayed fluorescence small molecule or the heat-activated delayed fluorescence polymer in an organic solvent are considered, wherein the organic solvent comprises at least one of tetrahydrofuran, toluene, dichloromethane, chlorobenzene and trichloromethane.
The thermally activated delayed fluorescence small molecule material, the polymer material, the organic electroluminescent device and the preparation method thereof will be further described with reference to the following specific examples.
Example 1
Synthesis of a Compound represented by the formula (15):
5.4g of 4-fluoro-4' -hydroxybenzophenone, 5.2g of potassium carbonate and 250mL of a dimethyl sulfoxide solvent were added to a 500mL three-necked flask, and stirred at room temperature for 20min, then 7.5g of bromododecane was added dropwise, and the mixture was heated under reflux for 5 hours. After the reaction, the reaction mixture was filtered while it was hot, and the filtrate was spin-dried and recrystallized from ethanol to obtain 9.8g of a white solid, which is the compound represented by the formula (15), in a yield of 80%.
Wherein the hydrogen nuclear magnetic resonance spectrum of the compound represented by the formula (15) is1H NMR(CDCl3):δ7.79(m,2H；2),7.78(d,3JHH＝8.9Hz,2H；3),7.15(t,3JHH＝8.6Hz,3JHF＝8.6Hz,2H；1),6.95(d,3JHH＝8.9Hz,2H；4),4.04(t,3JHH＝6.5Hz,2H；5),1.82(m,2H；6),1.47(m,2H；7),1.4–1.2(16H；8–15),0.88ppm(t,3JHH＝8.8Hz,3H；16).13C NMR(101MHz,CDCl3)δ194.10(s),166.29(s),163.78(s),162.95(s),134.53(d, J ═ 3.0Hz), 132.58-132.05 (m),129.76(s),115.39(s),115.17(s),114.10(s),77.34(s),77.02(s),76.70(s),68.33(s),31.91(s),29.60(dd, J ═ 7.0,2.6Hz),29.33(s),29.11(s),25.98(s),22.67(s),18.41(s),14.08 (s. + TOF-MS: 385.2561 (measured value), 384.5354 (calculated value).
Synthesis of a compound represented by formula (16):
6.0g of the compound represented by the formula (15), 3.6g of 9, 9-dimethylacridine and 7.7g of cesium carbonate were put into a 500mL three-necked flask, evacuated and purged with nitrogen three times, then 250mL of a dimethyl sulfoxide solvent was added thereto, stirred at room temperature for 30min and then heated to 150 ℃ to react for 24 hours. After the reaction, the reaction mixture was cooled to room temperature, added to ice water and extracted with chloroform, and the organic phase was dried by spinning and purified by column chromatography (eluent includes dichloromethane and petroleum ether, the volume ratio of dichloromethane to petroleum ether is 1:3) to obtain 5.8g of a pale green solid, which was recrystallized from methanol to obtain compound M1 represented by formula (16) with a yield of 65%.
Wherein the hydrogen nuclear magnetic resonance spectrum of the compound represented by the formula (16) is1H NMR(400MHz,CHCl3)dppm0.88(t,J＝6.65Hz,3H；21)1.13-1.36(m,16H；13-20)1.70(s,6H；9)1.76-1.89(m,4H；11-12)3.96-4.14(m,2H；10)6.33(d,J＝8.03Hz,2H,8)6.90-7.06(m,6H；2-4)7.41-7.55(m,4H；5-6)7.92(d,J＝8.78Hz,2H；7)8.02(d,J＝8.03Hz,2H；1).13C NMR (101MHz, CDCl3) δ 194.69(s),163.15(s),144.76(s),140.54(s),137.96(s),132.63(s),132.33(s),130.99(s),130.43(s),129.60(s),126.41(s),125.33(s),120.97(s),114.22(d, J ═ 2.7Hz),77.33(s),77.01(s),76.70(s),68.38(s),36.05(s),31.92(s),31.16(s), 29.76-29.27 (m),29.12(s),26.01(s),22.69(s),14.12(s) + TOF-MS: 574.3628 (measured value), 573.8210 (calculated value).
Synthesis of a compound represented by formula (17):
adding 4.3g of the compound shown in the formula (16) into a 500mL three-neck flask, adding 250mL of a mixed solvent which comprises glacial acetic acid and trichloromethane in equal volume, putting the mixed solvent into an ice-water bath, stirring until the compound shown in the formula (16) is completely dissolved, then adding N-bromosuccinimide (NBS) into the three-neck flask every 30min until the adding amount is 3.2g, and reacting in the ice-water bath in a dark place for 12 h. After the reaction was completed, the contents of the three-necked flask were slowly poured into a large amount of ice water, and the organic phase was spin-dried after repeated extraction with chloroform, and purified by column chromatography (eluent comprising dichloromethane and petroleum ether at a volume ratio of 1:2) to obtain 3.6g of a pale green solid, which was recrystallized from methanol to obtain the compound represented by formula (17) in a yield of 85%.
The nuclear magnetic resonance hydrogen spectrum of the compound represented by the formula (17) is1H NMR(400MHz,CHCl3)0.90(t,J＝6.27Hz,3H；20)1.19-1.42(m,16H；12-19)1.68(s,6H；8)1.85(quin,J＝6.59Hz,2H；11)3.94-4.18(m,2H；10)4.09(t,J＝6.27Hz,2H；9)6.20(d,J＝8.78Hz,2H；7)7.03(d,J＝8.03Hz,2H；2)7.11(d,J＝8.78Hz,2H；3)7.43(d,J＝7.53Hz,2H；4)7.55(s,2H；5)7.93(d,J＝8.03Hz,2H；6)8.04(d,J＝7.53Hz,2H；1).13C NMR (101MHz, CDCl3) δ 139.37(s),132.58(d, J ═ 12.4Hz),131.90(s),130.77(s),129.38(d, J ═ 6.4Hz),128.22(s),115.88(s),114.26(s),113.75(s), 219.43-29.26 (m),77.33(s),77.01(s),76.69(s),68.42(s),32.65(dd, J ═ 296.4,248.4Hz),29.11(s),26.00(s),22.69(s),14.12(s) + TOF-MS: 732.1817 (measured value), 731.6130 (calculated value).
Synthesis of a compound represented by formula (18):
the synthesis is carried out under strict anhydrous and anaerobic conditions, and the Yamamoto catalytic system is adopted in the invention.
In a glove box filled with nitrogen, 45.1mg of bis (1, 5-cyclooctadiene) nickel (0), 18.8. mu.L of 1, 5-cyclooctadiene, 25.6mg of 2, 2' -bipyridine and 0.4mL of dimethylformamide were placed in a 10mL first polymerization tube. 50.0mg of the compound represented by the formula (18) and 0.4mL of THF were charged into a second polymerization tube. And heating and stirring the first polymerization tube at 50 ℃ for 30min, then transferring the substances in the second polymerization tube into the first polymerization tube by using a syringe, heating and stirring at 80 ℃ for 48h, then adding 10mL of bromobenzene for end capping, and reacting for 12h to obtain a mixed product. After the polymerization, the mixed product was diluted with an appropriate amount of chloroform and back-dropped in 150mL of a mixed solvent (the mixed solvent includes hydrochloric acid, methanol, and acetone in equal volumes) with a glass dropper and stirred for 2 hours, the solid mixture on the filter paper was collected after the filtration on the filter paper, and the solid mixture was dried overnight in a vacuum drying oven at 40 ℃ to obtain a dried solid mixture. Finally, the dried solid mixture was subjected to soxhlet extraction with methanol and acetone in this order for 24 hours, and finally dissolved in chloroform of HPLC purity and then spin-dried to obtain 35.0mg of a yellow-green polymer, which is a compound represented by formula (18), i.e., P1, with a yield of 70%. The molecular weight of compound P1 represented by formula (18) was measured by Gel Permeation Chromatography (GPC), wherein Mw was 642200 and PDI was 9.51.
The route of the above reaction is as follows:
Figure BDA0002721926750000161
FIG. 1 is a graph of the distribution of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) for M1, P1. As can be seen from the figure, the LUMO and HOMO of M1 and P1 are distributed on the benzophenone acceptor group and the acridine donor group respectively, have no overlap and are separated well, so that the fluorescent material has the potential of being a heat-activated delayed fluorescent material.
FIG. 2 is the thermogravimetric plot of M1, P1. As can be seen from the figure, the temperatures of M1 and P1 at 5% weight loss were 355 ℃ and 398 ℃ respectively, which indicates that both have good thermal stability and are suitable as light-emitting layer materials of organic light-emitting diodes.
FIG. 3 shows the UV-visible absorption spectra of M1 and P1 in the solution state and in the thin film state. M1 has an absorption peak at 300nm due to electron pi-pi + orbital transition in a solution state, M1 has an absorption peak at 368nm due to tight molecular packing and enhanced conjugation effect, which promotes enhanced Intramolecular Charge Transfer (ICT). Since charge transfer in P1 molecule is very strong, absorption peaks at 300nm and 368nm are observed in both solution state and thin film state, and the intensity is substantially the same.
FIG. 4 shows fluorescence spectra of M1 and P1 in a solvent state and a thin film state. M1 has an absorption peak at 474nm in the solution state and an absorption peak at 518nm in the thin film state; p1 has an absorption peak at 520nm in the solution state and at 563nm in the thin film state.
FIG. 5 is a fluorescence spectrum of M1 in different solvents. As can be seen from the figure, M1 has different absorption peaks in different solvents, has a solvent discoloration effect, and meets the typical characteristics of the thermally active delayed fluorescent material. Wherein A is the absorption curve of M1 in Chlorobenzene (CB), and M1 is yellow-green in chlorobenzene; b is the absorption curve of M1 in Tetrahydrofuran (THF), M1 is green in tetrahydrofuran; c is the absorption curve of M1 in Tolyl (TOL) with M1 in tolyl as blue; d is the absorption curve of M1 in trichloromethane (CHF), M1 is brown in trichloromethane; e is the absorption curve of M1 in Dichloromethane (DCM) and M1 is orange in dichloromethane.
FIG. 6 is a fluorescence spectrum of P1 in different solvents. As can be seen from the figure, P1 has different absorption peaks in different solvents, has a solvent discoloration effect, and conforms to the typical characteristics of the heat-active delayed fluorescent material. Wherein A is the absorption curve of P1 in Chlorobenzene (CB), P1 is brown in chlorobenzene; b is the absorption curve of P1 in Tetrahydrofuran (THF), P1 is orange in tetrahydrofuran; c is the absorption curve of P1 in Tolyl (TOL) and P1 is yellowish green in tolyl; d is the absorption curve of P1 in trichloromethane (CHF), P1 is dark blue in trichloromethane; e is the absorption curve of P1 in Dichloromethane (DCM) and P1 is dark blue in dichloromethane.
FIG. 7 is a fluorescence/phosphorescence plot for M1. The maximum external quantum efficiency (Δ EST) of M1 was calculated to be 0.04eV, which is advantageous for delaying the rapid up-conversion of triplet excitons to singlet excitons during fluorescence
FIG. 8 is a fluorescence/phosphorescence plot for P1. The maximum external quantum efficiency (Δ EST) of P1 was calculated to be 0.02eV, which is advantageous for delaying the rapid up-conversion of triplet excitons to singlet excitons during fluorescence.
Example 2
Synthesis of a compound represented by formula (19):
5.4g of 4-fluoro-4' -hydroxybenzophenone, 5.2g of potassium carbonate and 250mL of acetone solvent were added to a 500mL three-necked flask, and stirred at room temperature for 20min, after which 7.5g of bromodecane was added dropwise and the mixture was heated under reflux for 5 hours. After the reaction, the reaction mixture was filtered while it was hot, and the filtrate was spin-dried and recrystallized from ethanol to obtain 9.8g of a white solid, which is the compound represented by formula (19), in a yield of 80%.
Synthesis of a compound represented by formula (20):
6g of the compound represented by the formula (19), 3.6g of 9, 9-dimethylacridine and 7.7g of cesium carbonate were put into a 500mL three-necked flask, evacuated and purged with nitrogen three times, then 250mL of a dimethylsulfoxide solvent was added, stirred at room temperature for 30 minutes, and then heated to 150 ℃ to react for 24 hours. After the reaction, the reaction mixture was cooled to room temperature, added to ice water and extracted with chloroform, and the organic phase was dried by spinning and purified by column chromatography (eluent includes dichloromethane and petroleum ether, the volume ratio of dichloromethane to petroleum ether is 1:3) to obtain 5.8g of a pale green solid, which was recrystallized from methanol to obtain compound M2 represented by formula (20) with a yield of 65%.
Synthesis of a Compound represented by the formula (21):
adding 4.3g of the compound shown in the formula (20) into a 500mL three-neck flask, adding 250mL of a mixed solvent which comprises glacial acetic acid and trichloromethane in equal volume, putting the mixed solvent into an ice-water bath, stirring until the compound shown in the formula (20) is completely dissolved, then adding N-bromosuccinimide (NBS) into the three-neck flask every 30min until the adding amount is 3.2g, and reacting in the ice-water bath in a dark place for 12 h. After the reaction was completed, the contents of the three-necked flask were slowly poured into a large amount of ice water, and the organic phase was spin-dried after repeated extraction with chloroform, and purified by column chromatography (eluent comprising dichloromethane and petroleum ether at a volume ratio of 1:2) to obtain 3.6g of a pale green solid, which was recrystallized from methanol to obtain the compound represented by the formula (21) in a yield of 85%.
Synthesis of a compound represented by formula (22):
the synthesis is carried out under strict anhydrous and anaerobic conditions, and a Yamamoto catalytic system is adopted.
In a glove box filled with nitrogen, 45.1mg of bis (1, 5-cyclooctadiene) nickel (0), 18.8. mu.L of 1, 5-cyclooctadiene, 25.6mg of 2, 2' -bipyridine and 0.4mL of dimethylformamide were placed in a 10mL first polymerization tube. 50mg of the compound represented by the formula (22) and 0.4mL of THF were charged into a second polymerization vessel. And heating and stirring the first polymerization tube at 50 ℃ for 30min, then transferring the substances in the second polymerization tube into the first polymerization tube by using a syringe, heating and stirring at 80 ℃ for 48h, then adding 10mL of bromobenzene for end capping, and reacting for 12h to obtain a mixed product. After the polymerization, the mixed product was diluted with an appropriate amount of chloroform and back-dropped in 150mL of a mixed solvent (the mixed solvent includes hydrochloric acid, methanol, and acetone in equal volumes) with a glass dropper and stirred for 2 hours, the solid mixture on the filter paper was collected after the filtration on the filter paper, and the solid mixture was dried overnight in a vacuum drying oven at 40 ℃ to obtain a dried solid mixture. Finally, the dried solid mixture was subjected to soxhlet extraction with methanol and acetone in this order for 24 hours, and finally dissolved in chloroform of HPLC purity and then spin-dried to obtain 35.0mg of a yellow-green polymer, which is a compound represented by formula (22), i.e., P2, with a yield of 70%. The molecular weight of compound P2 represented by formula (18) was measured by Gel Permeation Chromatography (GPC), wherein Mw was 642200 and PDI was 9.51.
The route of the above reaction is as follows:
Figure BDA0002721926750000191
application example 1
Preparing PEDOT, namely a PSS hole injection layer, a light-emitting layer, a DPEPO hole blocking layer, a TmPyPB electron transport layer, a LiF electron injection layer and an Al cathode layer on the ITO anode layer in sequence; the preparation of the light-emitting layer comprises mixing light-emitting layer main body materials of CZAcSF, M1, an exciton blocking layer material of mCP and tetrahydrofuran to obtain an intermediate; and after spin coating, the intermediate is heated to 100 ℃ and maintained for 10min to obtain the luminescent layer, and the organic electroluminescent device with the structure shown in the figure 9 is prepared (ITO/PEDOT: PSS/CzAcSF/M1/mCP/DPEPO/TmPyPB/LiF/Al).
Application example 2
Preparing PEDOT, namely a PSS hole injection layer, a light-emitting layer, a DPEPO hole blocking layer, a TmPyPB electron transport layer, a LiF electron injection layer and an Al cathode layer on the ITO anode layer in sequence; the preparation of the light-emitting layer comprises mixing light-emitting layer main body materials of CZAcSF and P1, an exciton blocking layer material of mCP and tetrahydrofuran to obtain an intermediate; and after spin coating, the intermediate is heated to 100 ℃ and maintained for 10min to obtain the luminescent layer, and the organic electroluminescent device with the structure shown in the figure 10 is prepared (ITO/PEDOT: PSS/CzAcSF/P1/mCP/DPEPO/TmPyPB/LiF/Al).
Fig. 11 is an electroluminescence spectrum of the organic light emitting electroluminescent device of application example 1 and the organic light emitting electroluminescent device of application example 2. As can be seen from the figure, the organic light-emitting electroluminescent device of application example 1 had an absorption peak of 450nm, and the organic light-emitting electroluminescent device of application example 2 had an absorption peak of 537 nm.
Fig. 12 is a current density-voltage curve of the organic light emitting electroluminescent device of application example 1 and the organic light emitting electroluminescent device of application example 2. As can be seen from the figure, the current density of the organic light emitting device of application example 1 can reach 90mA/cm2The current density of the organic light-emitting device of application example 2 can reach 95mA/cm2。
Fig. 13 is a graph of luminous intensity versus voltage for the organic light emitting electroluminescent device of application example 1 and the organic light emitting electroluminescent device of application example 2. As can be seen from the figure, the luminous intensity of the organic electroluminescent device of application example 1 can reach 4000cd/m2The luminous intensity of the organic electroluminescent device of application example 2 can reach 5000cd/m2。
Fig. 14 is a current density-external quantum efficiency curve of the organic light emitting electroluminescent device of application example 1 and the organic light emitting electroluminescent device of application example 2. As can be seen from the figure, the organic light emitting electroluminescent device of application example 1 and the organic light emitting electroluminescent device of application example 2 both have high external quantum efficiency, the external quantum efficiency of the organic light emitting electroluminescent device of application example 1 can reach 15%, and the external quantum efficiency of the organic light emitting electroluminescent device of application example 2 can reach 5%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A thermally activated delayed fluorescence small molecule material is characterized in that the structural formula of the thermally activated delayed fluorescence small molecule material is shown as formula (1):
Figure DEST_PATH_IMAGE001
，
wherein R is1Is selected from C12H25。
2. A thermally activated delayed fluorescence polymer material is characterized in that the structural formula of the thermally activated delayed fluorescence polymer material is shown as formula (2):
Figure 583508DEST_PATH_IMAGE002
，
wherein n is 1120, R1Is selected from C12H25，R2Is selected from any one of N-hexyl carbazolyl, phenylethynyl styryl and phenyl.
3. The thermally activated delayed fluorescence polymer material of claim 2, wherein the structural formula of the thermally activated delayed fluorescence polymer material is as shown in formula (3):
Figure DEST_PATH_IMAGE003
。
4. an organic electroluminescent device comprising a cathode layer, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, a hole injection layer and an anode layer, which are sequentially stacked, wherein the light emitting layer comprises the thermally activated delayed fluorescence small molecule material according to claim 1 or the thermally activated delayed fluorescence polymer material according to claim 2 or 3.
5. A method for manufacturing an organic electroluminescent device, comprising:
preparing a hole injection layer, a luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode layer on the anode layer in sequence to obtain an organic electroluminescent device;
wherein the preparation of the light-emitting layer comprises mixing a light-emitting layer host material, an exciton blocking layer material, the thermally activated delayed fluorescence small molecule material of claim 1 or the thermally activated delayed fluorescence polymer material of claim 2 or 3, and an organic solvent to obtain an intermediate; and
and carrying out spin coating on the intermediate and then carrying out annealing treatment to obtain the light-emitting layer.
6. The method of claim 5, wherein the annealing comprises heating the intermediate at a temperature of 25 ℃ to 150 ℃ for a time of 0min to 60 min.
7. The method of claim 5, wherein the mass ratio of the host material of the light-emitting layer, the exciton blocking layer material, the thermally activated delayed fluorescence small molecule material of claim 1 or the thermally activated delayed fluorescence polymer material of claim 2 or 3 is (40-60): (20-40): (10-30).
8. The method of claim 5, wherein the organic solvent is at least one of tetrahydrofuran, toluene, dichloromethane, chlorobenzene, and chloroform.
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