CN112300056A - Green thermal activation delayed fluorescent material and preparation method thereof - Google Patents
Green thermal activation delayed fluorescent material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- C09K2211/10—Non-macromolecular compounds
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Abstract
The invention relates to a green thermal activation delayed fluorescence material with non-doping property and a preparation method thereof, and the material is 3, 5-di (9H-carbazole-9-yl) -2,4, 6-tri (3, 6-di-tert-butyl-9H-carbazole-9-yl) benzonitrile. The compound provided by the invention has a large torsion angle between a donor and an acceptor, has the characteristic of Twisted Internal Charge Transfer (TICT), has the advantages of typical heat-activated delayed fluorescence (TADF) property, high fluorescence quantum yield (PLQY) of 100%, high thermal stability and the like, and more importantly, the compound has no Aggregation Concentration Quenching (ACQ) effect in a pure film state. And the synthesis and preparation steps are few, the raw materials are easy to obtain, the synthesis and purification process is simple, the yield is high, and the large-scale synthesis and preparation can be realized.
Description
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to a thermal activation delayed fluorescent material with industrialization and good performance and an electroluminescent device thereof.
Background
Organic Light Emitting Diodes (OLEDs) are attracting much attention due to their great applications in light sources, flexible flat panel displays. The first generation of light emitting devices OLEDs based on conventional fluorescent materials showed Internal Quantum Efficiencies (IQE) as high as 25% and External Quantum Efficiencies (EQE) of 5-7.5%, since the emissive material can only obtain singlet excitons. The second generation phosphorescent material containing noble metal atoms can effectively utilize singlet excitons and triplet excitons to carry out spin-orbit coupling, and the IQE can reach 100%; however, in view of their rarity and high cost, iridium (Ir) and platinum (Pt) have been largely limited in their applications in the field of organic light emitting materials. The third generation light emitting material, a Thermally Activated Delayed Fluorescence (TADF) material, which is emerging in recent years, does not contain metal, and the TADF material can pass triplet excitons from the lowest triplet excited state (T)1) By intersystem crossing to the singlet excited state (S)1) In addition, the conversion of the light into photons can also reach 100% so that the light is a substitute of phosphorescent light-emitting materials with great potential and wide prospect, and therefore, the light has attracted great attention in the field of organic electroluminescence in the past years.
Most TADF materials suffer from serious Aggregation Concentration Quenching (ACQ) phenomenon, and are doped in a host material as a guest material in low concentration when an OLED device is prepared.
Disclosure of Invention
The invention discloses a high-efficiency green thermal activation delayed fluorescent material and a preparation method thereof, wherein the chemical name of the thermal activation delayed fluorescent material is 3, 5-di (9H-carbazole-9-yl) -2,4, 6-tri (3, 6-di-tert-butyl-9H-carbazole-9-yl) benzonitrile, and the material is used for solving the problems of serious concentration quenching phenomenon of the thermal activation delayed fluorescent material and low efficiency of a non-doped electroluminescent device; meanwhile, the problems that the existing TADF material has multiple synthesis and preparation steps, expensive raw materials, complex synthesis and purification process, low yield and difficult large-scale mass production are solved; in particular, the OLED prepared by doping the high-concentration light-emitting layer of the thermally activated delayed fluorescence material achieves the aims that the EQE of the OLED exceeds 20% and the roll-off is low in efficiency.
The thermal activation delayed fluorescence material is 3, 5-di (9H-carbazole-9-yl) -2,4, 6-tri (3, 6-di-tert-butyl-9H-carbazole-9-yl) benzonitrile, and the chemical formula is as follows: c91H88N6The chemical structural formula is as follows:
the preparation method of the thermal activation delayed fluorescence material comprises the following steps: 2,3,4,5, 6-pentafluorophenylnitrile, 3, 6-di-tert-butyl-9H-carbazole and 9H-carbazole are used as raw materials, and the green thermal activation delayed fluorescence material is prepared by continuous one-pot reaction; the reaction can be referred to as follows:
after the reaction is finished, pouring the reaction liquid into water, then carrying out suction filtration to obtain a large amount of solid, and separating and purifying the product by adopting a column chromatography (petroleum ether/dichloromethane, volume ratio of 4: 1) method to obtain the thermal activation delayed fluorescent material.
The invention discloses application of the thermal activation delayed fluorescence material in preparation of an organic electroluminescent device. The light-emitting layer of the organic electroluminescent device comprises the thermal activation delayed fluorescence material, and the thermal activation delayed fluorescence material is used as a guest material and doped with a host material to be used as the light-emitting layer or directly used as the light-emitting layer; furthermore, the doping concentration of the thermal activation delayed fluorescence material is 10-100 wt%.
The organic electroluminescent device based on the thermal activation delayed fluorescence material disclosed by the invention is characterized in that Indium Tin Oxide (ITO) is used as an anode, and the thickness of the double-pyrazino [2, 3-f: 2', 3' -H ] quinoxaline-2, 3,6,7,10, 11-Hexanenitrile (HATCN) is used as a Hole Injection Layer (HIL), 4' - (cyclohexane-1, 1-diyl) bis (N, N-di-p-Tolylaniline) (TAPC) is used as a Hole Transport Layer (HTL), 1, 3-bis (9H-carbazol-9-yl) benzene (mCP) is used as an electron/Exciton Blocking Layer (EBL), the thermally activated delayed fluorescence material is used as a guest material doped with 1, 3-bis (9H-carbazol-9-yl) benzene (mCP) host material and jointly used as a light emitting layer (EML), 4, 6-bis (3, 5-di (pyridin-3-yl) phenyl) -2-methylpyrimidine (PYTMPB) is used as an Electron Transport Layer (ETL), Lithium fluoride (LiF) was used as the Electron Injection Layer (EIL), aluminum (Al) was used as the cathode; further, the specifications of each layer of the organic electroluminescent device are as follows: ITO/HATCN (10 nm)/TAPC (60 nm)/mCP (10 nm)/mCP: TADF material (X wt%) (30 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm).
The invention provides a synthetic preparation method of a novel thermal activation delayed fluorescent material; and an OLED based on the thermally activated delayed fluorescence material, achieving the goal of low efficiency roll-off with EQE exceeding 20%; the method is used for solving the problems of serious concentration quenching phenomenon of the thermal activation delayed fluorescent material and low efficiency of the undoped electroluminescent device; meanwhile, the problems that the existing TADF material has multiple synthesis and preparation steps, expensive raw materials, complex synthesis and purification process, low yield and difficult large-scale mass production are solved.
There is no particular limitation on the preparation method of the organic electroluminescent device formed based on the thermally activated delayed fluorescence material according to the present invention and other raw materials. The organic film formed by the invention has high surface smoothness, stable chemical and physical properties, high luminous efficiency and low concentration quenching property, and the formed organic electroluminescent device has excellent performance.
The invention has the following beneficial effects:
1. the 3, 5-bis (9H-carbazole-9-yl) -2,4, 6-tris (3, 6-di-tert-butyl-9H-carbazole-9-yl) benzonitrile thermal activation delayed fluorescence material provided by the invention has the characteristic of distorted internal charge transfer (TICT), and has the advantages of thermal activation delayed fluorescence property (TADF), high fluorescence quantum yield (PLQY) of 100%, good thermal stability, no Aggregation Concentration Quenching (ACQ) effect in a pure film state and the like.
2. The OLED device based on the thermal activation delayed fluorescence material has the advantages of low driving voltage, high luminous brightness and high luminous stability, the external quantum efficiency EQE of a doped device is as high as 26.8%, the external quantum efficiency EQE of an undoped device is as high as 21.8%, the external quantum efficiency EQE of an ultra-thick undoped device (80 nm luminous layer) is as high as 21.0%, and in addition, the efficiency roll-off of the devices is very small.
3. The thermally activated delayed fluorescence material provided by the invention has the advantages of few synthesis and preparation steps, cheap and easily available raw materials, simple synthesis and purification process, high yield and large-scale synthesis and preparation. The organic electroluminescent device based on the organic electroluminescent material has great application prospect and economic value in the fields of illumination, flat panel display and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound A prepared in example 1;
FIG. 2 is a nuclear magnetic carbon spectrum of Compound A prepared in example 1;
FIG. 3 is a mass spectrum of Compound A prepared in example 1;
FIG. 4 is an efficiency diagram of an embodiment device;
FIG. 5 is a graph of the efficiency of an undoped device of Compound A;
figure 6 is a graph of the efficiency of an undoped device of compound B.
Detailed Description
The raw materials involved in the invention are all conventional commercial products, and the specific operation method and the test method are conventional methods in the field; the specific preparation process of the organic electroluminescent device based on the thermal activation delayed fluorescence material and the materials of each layer are the prior art, such as vacuum evaporation, the vacuum degree is less than or equal to 2 multiplied by 10-4 Pa, the deposition rate of the functional layer is 2A/s, the deposition rate of the host material is 1A/s, the deposition rate of the LiF layer is 0.1A/s, and the deposition rate of Al8A/s. The invention creatively provides a novel thermal activation delayed fluorescence material with non-doping property, and a doped host material or a non-doped host material is independently used as a light-emitting layer of an organic electroluminescent device.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the descriptions are intended to further illustrate the features and advantages of the invention and are not intended to limit the scope of the claims which follow
The invention provides a high-efficiency green thermal activation delayed fluorescence material 3, 5-di (9H-carbazole-9-yl) -2,4, 6-tri (3, 6-di-tert-butyl-9H-carbazole-9-yl) benzonitrile (compound A).
The structural formula is as follows:
example 1
The reaction formula is as follows:
the reaction is as follows:
adding 3.50 g (12.52 mmol) of 3, 6-di-tert-butyl-9H-carbazole and 15 mL of N, N' -Dimethylformamide (DMF) into a 150 mL three-neck flask, adding 0.26 g (10.83 mmol) of NaH under the condition of ice bath, and then stirring for 30 minutes under the protection of nitrogen to obtain a mixed solution;
adding 1.50 g (8.97 mmol) of 9H-carbazole and 10 mL of DMF into a 150 mL three-neck flask, adding 0.22 g (9.12 mmol) of NaH under the ice bath condition, and stirring for 30 minutes under the protection of nitrogen to obtain a mixed solution;
adding the mixed solution into 30 mL of DMF containing 0.80 g (4.14 mmol) of 2,3,4,5, 6-pentafluorophenylnitrile, reacting for 12 hours at room temperature, adding the mixed solution, and heating for reaction for 12 hours at 120 ℃ under the protection of nitrogen; then pouring the reaction liquid into water, precipitating a large amount of solid, carrying out suction filtration, and separating and purifying the product by adopting a column chromatography (petroleum ether/dichloromethane, volume ratio is 4: 1) method to obtain a green solid 3, 5-bis (9H-carbazole-9-yl) -2,4, 6-tris (3, 6-di-tert-butyl-9H-carbazole-9-yl) benzonitrile, which is a compound A, with the yield of 53%.
FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound A obtained as described above; FIG. 2 shows the nuclear magnetic carbon spectrum of Compound A obtained as described above; FIG. 3 is a mass spectrum of Compound A obtained as described above. The structure detection of the compound A is as follows:
1H NMR (400 MHz, CDCl3) δ 7.66 (d, J = 1.5 Hz, 4H), 7.26 (d, J = 7.4 Hz, 4H), 7.23 (d, J = 1.8 Hz, 2H), 7.10 (d, J = 8.6 Hz, 4H), 7.04 (dd, J = 8.6, 1.8 Hz, 6H), 6.93 (d, J = 8.2 Hz, 4H), 6.77 (dd, J = 11.0, 3.9 Hz, 4H), 6.61 – 6.55 (m, 6H), 1.35 (s, 36H), 1.12 (s, 18H)；
13C NMR (101 MHz, CDCl3) δ 143.83, 143.42, 143.24, 141.11, 138.18, 137.62, 136.91, 136.02, 124.28, 124.13, 123.99, 123.80, 122.77, 121.96, 119.99, 118.97, 116.67, 115.99, 115.33, 110.46, 110.40, 109.98, 34.53, 34.21, 31.82, 31.57；
MALDI-TOF MS (ESI, m/z) calcd for C91H88N6 [M+]: 1264.71, Found: 1265.915。
from the above results, it was found that the structure of compound A was correct. The physical properties of compound a are shown in table 1.
The effect of the compound synthesized by the present invention as a material for a light emitting layer in a device is illustrated by the following application examples.
Application examples
(I) production and Performance evaluation of organic electroluminescent device having light-emitting layer A having a doping concentration of 10 wt%
The organic electroluminescent device with the doping concentration of 10 wt% and the A as the luminescent layer comprises the following manufacturing steps:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/mCP: 10 wt% A (30 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Evaluation of Performance of organic electroluminescent device having light emitting layer doped with A at a concentration of 10 wt%
Applying direct current to the manufactured organic electroluminescent device, and evaluating the luminescence performance by using an integrating sphere; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. Device performance is shown in table 2 and fig. 4.
(II) preparation and Performance evaluation of organic electroluminescent device with A as light emitting layer and 15 wt% doping concentration
The organic electroluminescent device with the doping concentration of 15 wt% and the A as the luminescent layer comprises the following manufacturing steps:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/mCP: 15 wt%A (30 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Evaluation of Performance of organic electroluminescent device having light emitting layer doped with 15 wt% of A
Applying direct current to the manufactured organic electroluminescent device, and evaluating the luminescence performance by using an integrating sphere; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. Device performance is shown in table 2 and fig. 4.
(III) preparation and Performance evaluation of organic electroluminescent device with A as light emitting layer and doping concentration of 20 wt%
The organic electroluminescent device with the doping concentration of 20 wt% and the A as the luminescent layer comprises the following manufacturing steps:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/mCP: 20 wt% A (30 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Evaluation of Performance of organic electroluminescent device having A as light emitting layer with doping concentration of 20 wt%
Applying direct current to the manufactured organic electroluminescent device, and evaluating the luminescence performance by using an integrating sphere; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. Device performance is shown in table 2 and fig. 4.
(IV) preparation and Performance evaluation of an organic electroluminescent device having A as a light-emitting layer with a doping concentration of 30 wt%
The organic electroluminescent device with the A as the luminescent layer and the doping concentration of 30 wt% is prepared by the following steps:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/mCP: 30 wt% A (30 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Evaluation of Performance of organic electroluminescent device having light emitting layer doped with 30 wt% of A
Applying direct current to the manufactured organic electroluminescent device, and evaluating the luminescence performance by using an integrating sphere; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. Device performance is shown in table 2 and fig. 4.
(V) preparation and Performance evaluation of organic electroluminescent device having A as light-emitting layer with doping concentration of 50 wt%
The organic electroluminescent device with the doping concentration of 50 wt% and the A as the luminescent layer comprises the following manufacturing steps:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/mCP: 50 wt% A (30 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Evaluation of Performance of organic electroluminescent device having light emitting layer doped with A at 50 wt%
Applying direct current to the manufactured organic electroluminescent device, and evaluating the luminescence performance by using an integrating sphere; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. Device performance is shown in table 2 and fig. 4.
(VI) preparation and Performance evaluation of an organic electroluminescent device having A as a light-emitting layer (i.e., having Compound A as the light-emitting layer alone) with a doping concentration of 100wt%
The organic electroluminescent device with the doping concentration of 100wt% and the A as the luminescent layer comprises the following manufacturing steps:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/100 wt% A (30 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Evaluation of Performance of organic electroluminescent device having light emitting layer A with doping concentration of 100wt%
Applying direct current to the manufactured organic electroluminescent device, and evaluating the luminescence performance by using an integrating sphere; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. Device performance is shown in table 2 and fig. 4.
(VII) preparation and performance evaluation of organic electroluminescent device with 80nm material A as luminescent layer
The organic electroluminescent device with the 80nm material A as the luminescent layer is manufactured by the following steps:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/A (80 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of organic electroluminescent device with 80nm material A as light-emitting layer
Applying direct current to the manufactured organic electroluminescent device, and evaluating the luminescence performance by using an integrating sphere; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. The device performance is shown in FIG. 5, the turn-on voltage is 3.0V, the maximum external quantum efficiency is 21.0%, and the electroluminescence peak value is 510 nm.
Comparative example
The preparation and performance evaluation of an organic electroluminescent device using the compound B with the wavelength of 80nm as a light-emitting layer (namely, only using the compound B as the light-emitting layer), and the preparation of the compound of the comparative example refer to the preparation method of the compound of the example.
The structural formula of compound B is as follows:
the manufacturing steps of the organic electroluminescent device with the luminescent layer B are as follows:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/B (80 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of organic electroluminescent device having 80nm Compound B as light-emitting layer
Applying direct current to the manufactured organic electroluminescent device, and evaluating the luminescence performance by using an integrating sphere; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. The device performance is shown in FIG. 6, the turn-on voltage is 3.5V, the maximum external quantum efficiency is 9.2%, and the electroluminescent peak value is 522 nm.
The organic electroluminescent device based on the material can emit sky blue to green fluorescence (the luminous peak value is 488 to 504 nm), the maximum external quantum efficiency of a doped device is as high as 26.8 percent, the maximum external quantum efficiency of an undoped device is as high as 21.8 percent, and the organic electroluminescent device based on the material has the advantages of low driving voltage, good luminous stability and the like. The organic electroluminescent device based on the organic electroluminescent material has great application prospect and economic value in the fields of illumination, flat panel display and the like.
Claims (10)
1. A green thermally activated delayed fluorescence material, characterized by: the chemical structural formula of the green thermally-activated delayed fluorescence material is as follows:
2. the method for preparing a green thermally activated delayed fluorescence material of claim 1, comprising the steps of: 2,3,4,5, 6-pentafluorophenylnitrile, 3, 6-di-tert-butyl-9H-carbazole and 9H-carbazole are used as raw materials to react to prepare the green thermal activation delayed fluorescence material 2,4, 6-tris (3, 6-di-tert-butyl-9H-carbazole-9-yl) -3, 5-difluorobenzonitrile.
3. The method for preparing a green thermally activated delayed fluorescence material according to claim 2, wherein the reaction is a continuous one-pot reaction.
4. The preparation method of the green thermally-activated delayed fluorescence material according to claim 2, wherein the molar ratio of 2,3,4,5, 6-pentafluorophenylnitrile, 3, 6-di-tert-butyl-9H-carbazole and 9H-carbazole is 1: 3 to 3.5: 2 to 2.5.
5. The method for preparing a green thermally activated delayed fluorescence material according to claim 2, wherein the reaction is performed in the presence of NaH under the protection of nitrogen.
6. The method for preparing a green thermally-activated delayed fluorescent material according to claim 2, wherein after the reaction is finished, the reaction solution is poured into water, and then the thermal-activated delayed fluorescent material is obtained by suction filtration, column chromatography separation and purification.
7. Use of a green thermally activated delayed fluorescence material according to claim 1 for the preparation of an organic electroluminescent device.
8. Use of the green thermally activated delayed fluorescence material of claim 1 in the preparation of a light emitting layer of an organic electroluminescent device.
9. The use according to claim 8, wherein the green thermally activated delayed fluorescence material is doped as a guest material with a host material as a light emitting layer, or directly as a light emitting layer.
10. The use according to claim 9, wherein the doping concentration of the green thermally activated delayed fluorescence material is 10 to 100 wt%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316924A (en) * | 2015-06-16 | 2017-01-11 | 清华大学 | Thermally activated delayed fluorescence material |
| CN108011040A (en) * | 2016-10-31 | 2018-05-08 | 昆山工研院新型平板显示技术中心有限公司 | A kind of green organic electrofluorescence device |
| CN110366548A (en) * | 2017-02-24 | 2019-10-22 | 国立大学法人九州大学 | Compound, luminescent material and light-emitting component |
| WO2020039708A1 (en) * | 2018-08-23 | 2020-02-27 | 国立大学法人九州大学 | Organic electroluminescence element |
-
2020
- 2020-10-30 CN CN202011194230.8A patent/CN112300056A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316924A (en) * | 2015-06-16 | 2017-01-11 | 清华大学 | Thermally activated delayed fluorescence material |
| CN108011040A (en) * | 2016-10-31 | 2018-05-08 | 昆山工研院新型平板显示技术中心有限公司 | A kind of green organic electrofluorescence device |
| CN110366548A (en) * | 2017-02-24 | 2019-10-22 | 国立大学法人九州大学 | Compound, luminescent material and light-emitting component |
| WO2020039708A1 (en) * | 2018-08-23 | 2020-02-27 | 国立大学法人九州大学 | Organic electroluminescence element |
Non-Patent Citations (2)
| Title |
|---|
| DONGDONG ZHANG 等: "Sterically shielded blue thermally activated delayed fluorescence emitters with improved efficiency and stability", 《MATERIALS HORIZONS》 * |
| YONG JOO CHO 等: "Molecular Engineering of High Efficiency and Long Lifetime Blue Thermally Activated Delayed Fluorescent Emitters for Vacuum and Solution Processed Organic Light-Emitting Diodes", 《ADVANCED OPTICAL MATERIALS》 * |
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