CN109897065B - 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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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
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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 thermally activated delayed fluorescent material has ultra-fast reverse intersystem crossing rate and high luminous efficiency, is a blue light TADF material with obvious TADF characteristics and high energy level, utilizes 100% internal quantum utilization efficiency of the TADF material, and is applied to an organic electroluminescent diode device as a main material of a traditional fluorescent material, so that the fluorescent device can achieve device efficiency comparable to that of a phosphorescent device of a phosphorescent heavy metal complex, the exciton utilization rate is greatly improved, and the problems of poor color gamut, overlong exciton service life and the like caused by directly using the TADF material as a luminescent layer material are solved.
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.
The organic electroluminescent material is used as a core component of an OLED device, and has great influence on the service performance of the device. The light emitting layer material of an OLED device generally comprises a mixture of host and guest materials, wherein 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 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. And due to the very wide nature of the TADF materialThe spectrum, and exciton lifetimes on the order of microseconds, greatly limit their application in mass-produced device structures.
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 high-energy-level blue TADF compound with remarkable TADF characteristics, and can be used as a main material of a luminous layer 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 bipolar heat activation delayed fluorescence material as a main material of a light-emitting layer, can achieve the device efficiency which is comparable to that of a phosphorescence device of a phosphorescence heavy metal complex, and solves the problems of poor color gamut, overlong exciton service life and the like caused by directly using a TADF material as a material of the light-emitting layer.
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 first formula, R represents a chemical group as an electron donor, and R is positioned at the ortho-position, the para-position or the meta-position of a phosphorus atom in a benzene ring.
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 1:1-2:0.02-0.1:0.1-0.2 into a reaction bottle, and reacting the mixture with the halogenated raw material in a ratio of 1-2: 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 in ortho, para or meta position of phosphorus atom in benzene ring;
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 compound containing the electron donor is 9, 10-dihydro-9, 9-diphenylacridine;
said halogenationThe raw materials are 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 host material and a guest material mixed, the host material being selected from the thermally activated delayed fluorescence materials as described above.
The light-emitting layer is formed by adopting a vacuum evaporation method or a solution coating method.
The guest material is PPA.
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, wherein each organic film layer comprises a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer, the hole injection layer is made of HATCN, the hole transport layer is made of TCTA, and the electron transport layer is made of TmPyPB.
Compared with the prior materials and technologies, the invention has the following advantages and beneficial effects:
(1) the thermally activated delayed fluorescent material has an ultra-fast reverse intersystem crossing rate and high luminous efficiency, is a high-energy-level blue light TADF compound with remarkable TADF characteristics, is easy to operate, and has high yield of the obtained target product;
(2) the organic electroluminescent diode device utilizes the 100% internal quantum utilization efficiency of the TADF material, and applies the thermal activation delayed fluorescent material as the main material of the traditional fluorescent material to the organic electroluminescent diode device, so that the fluorescent device can achieve the device efficiency which is comparable to that of a phosphorescent device of a phosphorescent heavy metal complex, the exciton utilization rate is greatly improved, and the problems of poor color gamut, overlong exciton service life and the like caused by directly using the TADF material as the luminescent layer material are solved.
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 the starting materials 1(2.68g, 5mmol), 9, 10-dihydro-9, 9-diphenylacridine (2.00g, 6mmol), palladium acetate Pb (OAc) (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (t-Bu)3HPBF4(0.17g, 0.6mmol), sodium tert-butoxide NaOt-Bu (0.58g, 6mmol) was added to the glove box, and 40mL of water previously removed were added under an argon atmosphereDeoxygenated toluene and reacted at 120 ℃ for 24 hours. Cooling to room temperature, pouring the reaction solution into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 3:1) to obtain 2.0g of compound 1 as a blue-white powder with a yield of 51%.
1HNMR(300MHz,CD2Cl2,δ):7.73(d,J＝6.3Hz,2H),7.38(d,J＝6.9Hz,2H),7.26-7.07(m,14H),6.95-6.83(m,4H)。
MS(EI)m/z:[M]+calcd for C43H22F10NOP,789.13；found,789.08。
Example 2:
the synthesis route of the target compound 2 is as follows:
a100 mL two-necked flask was charged with raw material 2(2.68g, 5mmol), 9, 10-dihydro-9, 9-diphenylacridine (2.00g, 6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6mmol), and then sodium tert-butoxide (0.58g, 6mmol) was added to the flask, and 40mL of toluene previously freed from water and oxygen was charged under an argon atmosphere, followed by reaction at 120 ℃ for 24 hours. Cooling to room temperature, pouring the reaction solution into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 3:1) to obtain 1.6g of compound 2 as a blue-white powder with a yield of 41%.
1H NMR(300MHz,CD2Cl2,δ):7.57(s,1H),7.43-7.33(m,3H),7.26-7.07(m,14H),6.95-6.83(m,4H)。
MS(EI)m/z:[M]+calcd for C43H22F10NOP,789.13；found,789.10。
Example 3:
the synthetic route for the target compound 3 is shown below:
a100 mL two-necked flask was charged with the starting materials 3(2.68g, 5mmol), 9, 10-dihydro-9, 9-diphenylacridine (2.00g, 6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6mmol), and then sodium tert-butoxide (0.58g, 6mmol) was added to the flask, and 40mL of toluene previously freed from water and oxygen was charged under an argon atmosphere, followed by reaction 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, 3:1) to obtain 1.0g of compound 3 as blue-white powder with a yield of 25%.
1H NMR(300MHz,CD2Cl2,δ):7.73(d,J＝6.9Hz,1H),7.54-7.38(m,2H),7.32(d,J＝6.3Hz,1H),7.26-7.07(m,14H),6.95-6.83(m,4H)。
MS(EI)m/z:[M]+calcd for C43H22F10NOP,789.13；found,789.11。
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 HATCN, the material of the hole transport layer 3 is TCTA, the material of the light emitting layer is a mixture of the thermally activated delayed fluorescent material of the present invention and PPA, the material of the electron transport layer 5 is TmPyPB, and the cathode is a double-layer structure composed of a lithium fluoride (LiF) layer and an aluminum (Al) layer.
Wherein HATCN refers to 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene, TCTA refers to 4,4' -tris (carbazol-9-yl) triphenylamine, PPA refers to 9-pyrenyl- (10) -4-triphenylanilinoanthracene, and TmPyPB refers to 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: on cleaned ITO glass, a 2 nm-thick HATCN film, a 35 nm-thick TCTA film, a thermally activated delayed fluorescent material added PPA, a 40 nm-thick TmPyPB film, a 1 nm-thick LiF film and a 100 nm-thick Al film are sequentially evaporated under a high vacuum condition. The device shown in fig. 3 is manufactured by the method, and various specific device structures are as follows:
device 1:
ITO/HATCN (2nm)/TCTA (35 nm)/Compound 1: PPA (20% 40nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm)
Device 2:
ITO/HATCN (2nm)/TCTA (35 nm)/Compound 2: PPA (20% 40nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm)
Device 3:
ITO/HATCN (2nm)/TCTA (35 nm)/Compound 3: PPA (20% 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 host materials for the light emitting layer
| Device with a metal layer | Maximum current efficiency (cd/A) | CIEy | Maximum external quantum efficiency (%) |
| |
23.5 | 0.09 | 22.3 |
| Device | |||
| 2 | 22.1 | 0.09 | 21.7％ |
| Device 3 | 19.3 | 0.09 | 19.9％ |
In table 2, CIEy is a y-coordinate value of the standard CIE color space.
In conclusion, a series of thermally activated delayed fluorescent materials with lower single/triplet state energy level difference, high luminous efficiency and fast reverse system crossing constant are synthesized through ingenious molecular design, the thermally activated delayed fluorescent materials are high-energy-level blue TADF materials with obvious TADF characteristics, the synthesis route is reasonably designed, and the yield of the obtained target product is higher.
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. The thermally activated delayed fluorescence material is characterized in that the thermally 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 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 1:1-2:0.02-0.1:0.1-0.2 into a reaction bottle, and reacting the mixture with the halogenated raw material in a ratio of 1-2: 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, and performing column chromatography separation and purification to obtain a product;
the structural general formula of the halogenated raw material is
Wherein Br is in ortho, para or meta position of phosphorus atom in benzene ring;
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
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 includes a host material selected from the thermally activated delayed fluorescence material of claim 1 and a guest material mixed.
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 of claim 3, wherein the guest material is PPA.
6. The organic electroluminescent diode device according to claim 3, 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, wherein each organic film layer comprises a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer, the hole injection layer is made of HATCN, the hole transport layer is made of TCTA, and the electron transport layer is made of TmPyPB.
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