CN110003208B - Thermal activation delayed fluorescent material, preparation method thereof and organic light-emitting diode device - Google Patents
Thermal activation delayed fluorescent material, preparation method thereof and organic light-emitting diode device Download PDFInfo
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
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Abstract
The invention relates to a thermal activation delayed fluorescent material, a preparation method thereof and an organic light-emitting diode device, wherein the structural general formula of the thermal activation delayed fluorescent material is shown as the following formula I: is like
R represents a chemical group as an electron donor. The thermal activation delayed fluorescent material has ultra-fast reverse intersystem crossing rate and high luminous efficiency, is a green light TADF material with obvious TADF characteristics, and therefore, when the thermal activation delayed fluorescent material is used as a luminous material to be applied to an organic electroluminescent diode device, the luminous efficiency of the organic electroluminescent diode device can be effectively improved, and the organic electroluminescent diode device based on the thermal activation delayed fluorescent material has very high device efficiency.
Description
Technical Field
The invention belongs to the technical field of electroluminescent materials, and particularly relates to a thermal activation delayed fluorescent material, a preparation method thereof and an organic electroluminescent diode device.
Background
An Organic Light-Emitting Diode (OLED) display panel attracts the attention of many researchers due to its advantages of no need of a backlight source for active Light emission, high Light-Emitting efficiency, large viewing angle, fast response speed, large temperature adaptation range, relatively simple production and processing technology, low driving voltage, low energy consumption, lightness, thinness, flexible display, and huge application prospect.
The principle of the OLED device is that under the action of an electric field, holes and electrons are respectively injected from an anode and a cathode, and are respectively compounded in a light-emitting layer through a hole injection layer, a hole transport layer, an electron injection layer and an electron transport layer to form excitons, and the excitons emit attenuated light.
Organic electroluminescent material as core component of OLED device, and its applicationThe performance has a great influence. The light-emitting layer of an OLED device generally contains a host material and a guest material, where the dominant light-emitting guest material is of critical importance. The light-emitting guest material used in the early OLED device is a fluorescent material, and since the exciton ratio of the singlet state to the triplet state in the OLED device is 1:3, the theoretical Internal Quantum Efficiency (IQE) of the OLED device based on the fluorescent material can only reach 25%, which greatly limits the application of the fluorescent electroluminescent diode device. The heavy metal complex phosphorescent material can realize 100% IQE by simultaneously using singlet and triplet excitons due to the spin-orbit coupling effect of heavy atoms. However, the commonly used heavy metals are noble metals such as iridium (Ir) and platinum (Pt), and the heavy metal complex phosphorescent light-emitting material has yet to be broken through in the aspect of blue light materials. The pure organic Thermal Activation Delayed Fluorescence (TADF) material has a molecular structure combining an electron donor (D) and an electron acceptor (A), and the molecules have smaller minimum single triplet energy level difference (delta E) through ingenious molecular designST) In this way, the triplet excitons can return to the singlet state by reverse intersystem crossing (RISC) and then jump to the ground state by radiation to emit light, so that both singlet and triplet excitons can be used, and 100% IQE can be realized.
Fast reverse intersystem crossing constant (k) for TADF materialsRISC) And high photoluminescence quantum yield (PLQY) are a necessary condition for the preparation of high efficiency OLED devices. At present, the TADF material with the above conditions is still deficient relative to the heavy metal Ir complex.
Disclosure of Invention
The invention aims to provide a thermally activated delayed fluorescent material, which has an ultra-fast reverse intersystem crossing rate and high luminous efficiency, is a green-light TADF compound with remarkable TADF characteristics and can be used as a luminous layer material of an organic electroluminescent diode.
Another object of the present invention is to provide a method for preparing a thermally activated delayed fluorescence material, which is easy to operate and can obtain a high yield of the target product.
The invention further aims to provide an organic light-emitting diode device, which adopts the thermal activation delayed fluorescence material as a light-emitting layer material, so that the light-emitting efficiency of the device is improved.
In order to achieve the above object, the present invention provides a thermally activated delayed fluorescence material having a chemical structure represented by the following formula:
is like
In the above formula I, R represents a chemical group as an electron donor, and R is at the 1 st, 2 nd or 4 th position in the pyridine group.
The chemical group R of the electron donor is selected from any one of the following groups:
the thermal activation delayed fluorescence material is a compound 1, a compound 2 or a compound 3, and the structural formulas of the compound 1, the compound 2 and the compound 3 are respectively as follows:
the invention also provides a preparation method of the thermal activation delayed fluorescent material, and the chemical synthesis route is as follows:
the method specifically comprises the following steps: adding a halogenated raw material, an electron donor-containing compound, palladium acetate and tri-tert-butylphosphine tetrafluoroborate in a molar ratio of 1:2-4:0.05-0.2:0.2-0.4 into a reaction bottle, and reacting the mixture with the halogenated raw material in a ratio of 2-4: 1, adding sodium tert-butoxide, adding toluene for removing water and oxygen in an argon atmosphere, and reacting at 110-130 ℃ for 20-30 hours; cooling to room temperature, pouring the reaction liquid into ice water, extracting, combining organic phases, spinning into silica gel, separating and purifying by column chromatography to obtain a product, and calculating the yield;
the structural general formula of the halogenated raw material is
Wherein Br is at the 1, 2 or 4 position in the pyridine group;
the structural general formula of the electron donor-containing compound is R-H, wherein R represents a chemical group used as an electron donor.
The chemical group R of the electron donor is selected from any one of the following groups:
the electron donor-containing compound is phenoxazine;
the halogenated raw material is raw material 1, raw material 2 or raw material 3, and the structural formulas of the raw material 1, the raw material 2 and the raw material 3 are respectively
The invention also provides an organic light-emitting diode device which comprises a substrate, a first electrode arranged on the substrate, an organic functional layer arranged on the first electrode and a second electrode arranged on the organic functional layer;
the organic functional layer comprises one or more organic film layers, and at least one organic film layer is a light-emitting layer;
the light emitting layer comprises a thermally activated delayed fluorescence material as described above.
The light-emitting layer is formed by adopting a vacuum evaporation method or a solution coating method.
The material of the light-emitting layer is a mixture of a host material and a guest material, and the guest material is selected from one or more of the thermal activation delayed fluorescence materials.
The substrate is a glass substrate, the first electrode is made of indium tin oxide, and the second electrode is a double-layer composite structure formed by a lithium fluoride layer and an aluminum layer;
the organic functional layer comprises a plurality of organic film layers, each organic film layer comprises a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer, wherein the hole injection layer is made of molybdenum trioxide, the hole transport layer is made of TCTA, the electron transport layer is made of TmPyPB, and the host material is mCBP.
Compared with the prior materials and technologies, the invention has the following advantages and beneficial effects:
(1) according to the invention, the position of the electron donor is subjected to isomerizing regulation, so that the luminous efficiency of the material is effectively increased, the influence of the position of the electron donor on the performance of the material is researched, and the green-light thermal activation delayed fluorescent material with obvious TADF (thermo-activated fluorescence) characteristics is designed;
(2) the thermal activation delayed fluorescent material is a sky blue TADF compound material with ultra-fast reverse intersystem crossing rate and high luminous efficiency, when the thermal activation delayed fluorescent material is used as a luminous material to be applied to an organic luminous display device, the luminous efficiency of the organic luminous display device can be improved, and an organic electroluminescent diode device based on the thermal activation delayed fluorescent material obtains very high device efficiency.
Drawings
The technical solution and other advantages of the present invention will become apparent from the following detailed description of specific embodiments of the present invention, which is to be read in connection with the accompanying drawings.
In the drawings, there is shown in the drawings,
FIG. 1 is a HOMO and LUMO energy level distribution diagram of compounds 1-3 prepared in examples 1-3 of the present invention;
FIG. 2 is a graph showing photoluminescence spectra of compounds 1 to 3 prepared in examples 1 to 3 of the present invention in a toluene solution at room temperature;
fig. 3 is a schematic structural diagram of an organic electroluminescent diode device according to the present invention.
Detailed Description
Some of the starting materials used in the present invention are commercially available materials. The preparation of some compounds will be described in the examples. The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1:
the synthesis route of the target compound 1 is as follows:
to a 100mL two-necked flask were added starting material 1(2.00g, 5mmol), phenoxazine (2.2g, 12mmol), palladium acetate Pb (OAc) (90mg, 0.4mmol), and tri-tert-butylphosphine tetrafluoroborate (t-Bu)3HPBF4(0.34g, 1.2mmol), sodium tert-butoxide NaOt-Bu (1.16g, 12mmol) was added to the glove box, and 60mL of toluene previously freed from water and oxygen were added under an argon atmosphere and reacted at 120 ℃ for 24 hours. Cooling to room temperature, pouring the reaction solution into 200mL of ice water, extracting with dichloromethane for three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 2:1) to obtain 1.6g of compound 1 as green powder with a yield of 53%.
1HNMR(300MHz,CD2Cl2,):8.54(s,2H),8.04(s,2H),7.62-7.48(m,5H),7.14-7.07(m,4H),7.03-6.96(m,12H)。
MS(EI)m/z:[M]+calcd for C40H25N5O2,607.20；found,607.18。
Example 2:
the synthesis route of the target compound 2 is as follows:
a100 mL two-neck flask was charged with starting material 2(2.00g, 5mmol), phenoxazine (2.2g, 12mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol), then sodium tert-butoxide (1.16g, 12mmol) was added in a glove box, 60mL of toluene previously freed from water and oxygen were added under argon atmosphere, and reacted at 120 ℃ for 24 hours. Cooling to room temperature, pouring the reaction solution into 200mL of ice water, extracting with dichloromethane for three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 2:1) to obtain 2.2g of compound 2 as green powder with a yield of 72%.
1H NMR(300MHz,CD2Cl2,):8.11(s,2H),7.62-7.48(m,5H),7.14-7.07(m,4H),7.03-6.96(m,12H),6.70(s,2H)。
MS(EI)m/z:[M]+calcd for C40H25N5O2,607.20；found,607.17。
Example 3:
the synthetic route for the target compound 3 is shown below:
a100 mL two-necked flask was charged with starting material 3(2.00g, 5mmol), phenoxazine (2.2g, 12mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol), then sodium tert-butoxide (1.16g, 12mmol) was added to the glove box, 60mL of toluene previously freed from water and oxygen were added under argon, and the reaction was carried out at 120 ℃ for 24 hours. Cooling to room temperature, pouring the reaction solution into 200mL of ice water, extracting with dichloromethane for three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 2:1) to obtain 1.3g of compound 3 as green powder with a yield of 43%.
1H NMR(300MHz,CD2Cl2,):8.14(s,2H),7.92(d,J＝6.3Hz,1H)7.14-7.07(m,4H),7.03-6.96(m,13H)。
MS(EI)m/z:[M]+calcd for C40H25N5O2,607.20；found,607.17。
While fig. 1 shows the orbital arrangement of compounds 1-3, it is evident from fig. 1 that the highest electron occupied orbital (HOMO) and the lowest electron unoccupied orbital (LUMO) of compounds 1-3 are arranged on different units, respectively, and complete separation is achieved, which helps to reduce the energy difference Δ EST between systems, thereby improving the reverse intersystem crossing capability. FIG. 2 shows photoluminescence spectra of compounds 1-3 in toluene solution at room temperature. For compounds 1-3, the simulations calculated the lowest singlet energy level S1 and the lowest triplet energy level T1 of the molecule.
The data for examples 1-3 are shown in Table 1. As can be seen from Table 1, the Delta Est of all the compounds is less than 0.3ev, the small energy level difference between the singlet state and the triplet state is realized, and the delayed fluorescence effect is obvious.
Table 1 photophysical property results for compounds 1-3
In table 1, PL Peak represents a photoluminescence Peak, S1 represents a singlet level, T1 represents a triplet level, and Δ EST represents a difference between the singlet and triplet levels.
Example 4:
preparation of organic electroluminescent diode (OLED) device:
as shown in fig. 1, the organic electroluminescent diode device using the thermally activated delayed fluorescence material as a guest material of a light-emitting layer according to the present invention may include a substrate 9, an anode layer 1, a hole injection layer 2, a hole transport layer 3, a light-emitting layer 4, an electron transport layer 5, and a cathode layer 6, which are sequentially disposed from bottom to top. The substrate 9 is a glass substrate, the anode 1 is made of Indium Tin Oxide (ITO), and the substrate 9 and the anode 1 jointly form ITO glass. The material of the hole injection layer 2 is molybdenum trioxide (MoO)3) The material of the hole transport layer 3 is TCTA, the material of the light emitting layer is a mixture of the activation delayed fluorescence compound of the present invention and mCBP, and the material of the electron transport layer 5 is TmPyPB. The cathode is a double-layer structure consisting of a lithium fluoride (LiF) layer and an aluminum (Al) layer.
Wherein TCTA means 4,4' -tris (carbazol-9-yl) triphenylamine, mCBP means 3,3' -bis (N-carbazolyl) -1,1' -biphenyl, TmPyPB means 1,3, 5-tris (3- (3-pyridyl) phenyl) benzene.
The organic light-emitting diode device can be manufactured according to a method known in the field, and the specific method comprises the following steps: after cleaned ITO glassSequentially evaporating MoO with the thickness of 2nm on glass under the high vacuum condition3The film, the TCTA film with the thickness of 35nm, the DPEPO plus activated delayed fluorescent compound, the Tm3PyPB film with the thickness of 40nm, the LiF film with the thickness of 1nm and the Al film with the thickness of 100 nm. The device shown in fig. 3 is manufactured by the method, and various specific device structures are as follows:
device 1:
ITO/MoO3(2nm)/TCTA (35 nm)/mCBP: compound 1 (5% 40nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm)
Device 2:
ITO/MoO3(2nm)/TCTA (35 nm)/mCBP: compound 2 (5% 40nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm)
Device 3:
ITO/MoO3(2nm)/TCTA (35 nm)/mCBP: compound 3 (5% 40nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm)
The current-luminance-voltage characteristics of the devices 1-3 were obtained with a Keithley source measurement system (Keithley 2400 source meter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes, the electroluminescence spectra were obtained with a SPEX CCD3000 spectrometer, JY, france, all in ambient air. The performance data for devices 1-3 are shown in table 2 below.
TABLE 2 Performance results for devices based on Compounds 1-3 as guest materials for the light emitting layer
| Device with a metal layer | Maximum current efficiency (cd/A) | CIEy | Maximum external quantum efficiency (%) |
| |
83.8 | 0.22 | 29.8 |
| Device | |||
| 2 | 88.7 | 0.24 | 30.9 |
| Device | |||
| 3 | 76.9 | 0.23 | 25.4％ |
In table 2, CIEy is a y-coordinate value of the standard CIE color space.
In conclusion, the position of the electron donor is subjected to isomeric regulation, so that the light-emitting efficiency of the material is effectively improved, the influence of the position of the electron donor on the performance of the material is researched, and finally, the organic electroluminescent diode device based on the target green TADF material obtains very high efficiency.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A heat-activated delayed fluorescence material is a compound 1, a compound 2 or a compound 3, and the structural formulas of the compound 1, the compound 2 and the compound 3 are respectively as follows:
2. a preparation method of a thermally activated delayed fluorescent material is characterized in that a chemical synthesis route is as follows:
the method specifically comprises the following steps: adding a halogenated raw material, an electron donor-containing compound, palladium acetate and tri-tert-butylphosphine tetrafluoroborate in a molar ratio of 1:2-4:0.05-0.2:0.2-0.4 into a reaction bottle, and reacting the mixture with the halogenated raw material in a ratio of 2-4: 1, adding sodium tert-butoxide, adding toluene for removing water and oxygen in an argon atmosphere, and reacting at 110-130 ℃ for 20-30 hours; cooling to room temperature, pouring the reaction liquid into ice water, extracting, combining organic phases, spinning into silica gel, separating and purifying by column chromatography to obtain a product, and calculating the yield;
the structural general formula of the halogenated raw material is
The structural general formula of the electron donor-containing compound is R-H, wherein R represents a chemical group used as an electron donor;
the electron donor-containing compound is phenoxazine;
the halogenated raw material is raw material 1, raw material 2 or raw material 3, and the structural formulas of the raw material 1, the raw material 2 and the raw material 3 are respectively
3. An organic electroluminescent diode device is characterized by comprising a substrate, a first electrode arranged on the substrate, an organic functional layer arranged on the first electrode and a second electrode arranged on the organic functional layer;
the organic functional layer comprises one or more organic film layers, and at least one organic film layer is a light-emitting layer;
the light-emitting layer contains the thermally activated delayed fluorescence material according to claim 1.
4. The organic electroluminescent diode device according to claim 3, wherein the light emitting layer is formed by vacuum evaporation or solution coating.
5. The organic electroluminescent diode device according to claim 3, wherein the material of the light emitting layer is a mixture of a host material and a guest material selected from one or more of the thermally activated delayed fluorescence materials according to claim 1.
6. The organic electroluminescent diode device according to claim 5, wherein the substrate is a glass substrate, the first electrode is made of indium tin oxide, and the second electrode is a two-layer composite structure of a lithium fluoride layer and an aluminum layer;
the organic functional layer comprises a plurality of organic film layers, each organic film layer comprises a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer, wherein the hole injection layer is made of molybdenum trioxide, the hole transport layer is made of TCTA, the electron transport layer is made of TmPyPB, and the host material is mCBP.
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