CN110015968A - Dark red photo-thermal activation delayed fluorescence material and preparation method thereof and electroluminescent device - Google Patents
Dark red photo-thermal activation delayed fluorescence material and preparation method thereof and electroluminescent device Download PDFInfo
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Abstract
The present invention provides a kind of dark red photo-thermal activation delayed fluorescence material and preparation method thereof and electroluminescent devices, the dark red photo-thermal activates delayed fluorescence (TADF) material, including the compound as composed by receptor A and donor D, the compound has general structure as shown in Equation 1: wherein the receptor A is to select from following structural any one to D-A formula 1:And the donor D is to select from following structural any one:
Description
Technical field
The present invention relates to field of display technology more particularly to a kind of dark red photo-thermal to activate delayed fluorescence (thermally
Activated delayed fluorescence, TADF) material and preparation method thereof and electroluminescent device.
Background technique
Organic electroluminescent LED (organic light-emitting diodes, OLED) display device is with its master
Dynamic shine does not need that backlight, luminous efficiency are high, visible angle is big, fast response time, Acclimation temperature range are big, production and processing work
The advantages that skill is relatively easy, driving voltage is low, and energy consumption is small, lighter and thinner, Flexible Displays and huge application prospect attract
The concern of numerous researchers.
Existing OLED display generally includes: substrate, the anode on substrate, the organic light emission on anode
Layer, the electron transfer layer on organic luminous layer and the cathode on electron transfer layer.It is sent out when work to organic luminous layer
The hole from anode and the electronics from cathode are penetrated, these electrons and holes is combined and generates excitability electron-hole pair, and
Excitability electron-hole pair is converted to ground state realization from excited state to shine.
In OLED, the light emitting guest material to play a leading role is most important.The light-emitting guest material that the OLED of early stage is used
Material is fluorescent material, since the exciton ratio of the singlet state in OLED and triplet is 1:3, the OLED based on fluorescent material
Theoretical internal quantum efficiency (internal quantum efficiency, IQE) can only achieve 25%, significantly limit glimmering
The application of photoelectricity electroluminescence device.Heavy metal complex phosphor material due to heavy atom Effect of Spin-orbit Coupling so that it
100% IQE can be realized using singlet state and triplet exciton simultaneously.However, usually used heavy metal is all Ir, Pt
Equal precious metals, cost is very high, and heavy metal complex phosphorescent light-emitting materials still need to be broken through in terms of blue light material.
Pure organic thermal activation delayed fluorescence (thermally activated delayed fluorescence, TADF) material
Material, by cleverly MOLECULE DESIGN, so that molecule has the lesser minimum triple energy level differences (Δ EST) of list, such triplet swashs
Son can return to singlet state by reversed intersystem crossing (RISC), then be shone by radiation transistion to ground state, so as to same
Shi Liyong is mono-, triplet exciton, and 100% IQE also may be implemented.
For TADF material, quickly reversed intersystem crossing constant (reverse intersystem-crossing,
KRISC) and high photoluminescence quantum yield (photoluminescence quantum yield, PLQY) is to prepare height
The necessary condition of efficiency OLED.Currently, green light and day blue light TADF material have obtained the external quantum efficiency more than 30%
(EQE)；But feux rouges and dark red smooth TADF material can not obtain excellent device due to energy gap rule (Energy gap law)
Performance.
Accordingly, it needs to develop a kind of dark red photo-thermal activation delayed fluorescence (TADF) material, molecule therein is with high
Between alter more rate constant and anti-intersystem crossing rate constant, and improve to the highest occupied molecular orbital (highest of receptor
Occupied molecular orbital, HOMO) and minimum molecular orbital (lowest unoccupied is not accounted for
Molecular orbital, LUMO) overlapping degree, to improve the device efficiency of TADF molecule.
Summary of the invention
The purpose of the present invention is to provide a kind of dark red photo-thermal to activate delayed fluorescence (thermally activated
Delayed fluorescence, TADF) material by cleverly MOLECULE DESIGN synthesized a series of depth of receptors containing quinones
Feux rouges thermal activation delayed fluorescence molecule.And this kind of molecular receptor contains carbonyl structure, so that molecule has high intersystem crossing speed
Rate constant and anti-intersystem crossing rate constant can effectively inhibit the reduction of the radiation transistion rate as caused by energy gap rule,
To obtain high photoluminescence quantum yield (photoluminescence quantum yield, PLQY).Pass through tune simultaneously
Position of the carbonyl in linear aromatic structure is saved, is improved to highest occupied molecular orbital (the highest occupied of receptor
Molecular orbital, HOMO) and minimum molecular orbital (lowest unoccupied molecular is not accounted for
Orbital, LUMO) overlapping degree, be capable of effectively suppression device efficiency roll-off, thus improve TADF molecule device effect
Rate prepares a series of high performance dark red smooth TADF Organic Light Emitting Diodes using these luminescent materials provided by the present invention
(organic light-emitting diodes, OLED).
To achieve the above object, the present invention provides a kind of dark red photo-thermal activation delayed fluorescence (TADF) materials, including by
Compound composed by receptor A and donor D, the compound have general structure as shown in Equation 1:
D-A formula 1
Wherein the receptor A is to select from following structural any one:
And
The donor D is to select from following structural any one:
The present invention also provides a kind of preparation methods of dark red photo-thermal activation delayed fluorescence (TADF) material, including walk as follows
It is rapid:
Step S10, compound A-X and compound D-B (OH) 2 is added in the solution containing alkali, wherein the X is halogen,
The A is with any one in following structural:
The D is with any one in following structural:
Step S20, under an inert gas, palladium catalyst is added in Xiang Suoshu solution, reacts the first duration at the first temperature
To obtain a reaction solution；
Step S30, the reaction solution is cooled to second temperature, obtains a mixture；And
Step S40, isolate described dark red photo-thermal activation delayed fluorescence (TADF) material from the mixture, including by by
Compound composed by body A and donor D, the compound have general structure as shown in Equation 1:
D-A formula 1.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, first temperature is 55 DEG C to 65 DEG C, and described first when is 12 hours to 36 hours a length of.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, the second temperature is room temperature.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, in the step S10, the solution is toluene, the alkali is potassium carbonate and the palladium catalyst is four triphenyl phosphorus
Palladium.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, the step S30, which is further included, passes through extraction, washing, dehydration, filtering and centrifugal drying processing for the reaction solution to obtain
To the mixture.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, step S40 system is separated using col-umn chromatography, and leacheate used by the col-umn chromatography is volume ratio 1:1's
Petroleum ether: methylene chloride.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, the compound A-X is 2- bromo aphthacene diketone 2- bromo pentacene -5,7,12,14- tetrones, the compound D-B
(OH) 2 be 4- (diphenyl amino)-phenyl boric acid.
The present invention provides a kind of electroluminescent device again, comprising: basal layer；Hole injection layer is located on the basal layer；
Hole transmission layer is located on the hole injection layer；Luminescent layer is located on the hole transmission layer；Electron transfer layer is located at institute
It states on luminescent layer；And cathode layer, it is located on the electron transfer layer, wherein the luminescent layer includes depth provided by the present invention
Feux rouges thermal activation delayed fluorescence (TADF) material.
An embodiment according to the present invention, in the electroluminescent device, the material of the basal layer includes ITO；Institute
The material for stating hole injection layer includes six cyano -1,4,5,8,9,12- of 2,3,6,7,10,11-, six azepine benzophenanthrene (HATCN)；
The material of the hole transmission layer includes 4,4'- cyclohexyl two [N, N- bis- (4- aminomethyl phenyl) aniline] (TAPC)；The electronics
The material of transport layer includes 1,3,5- tri- (3- (3- pyridyl group) phenyl) benzene (Tm3PyPB)；And the material packet of the cathode layer
Include lithium fluoride and aluminium.
Detailed description of the invention
It, below will be to embodiment or the prior art in order to illustrate more clearly of embodiment or technical solution in the prior art
Attached drawing needed in description is briefly described, it should be apparent that, the accompanying drawings in the following description is only some of invention
Embodiment for those of ordinary skill in the art without creative efforts, can also be attached according to these
Figure obtains other attached drawings.
Fig. 1 is the flow chart that the dark red photo-thermal of the embodiment of the present invention activates the preparation method of delayed fluorescence (TADF) material.
Fig. 2 is the fluorescence emission spectrum of compound 1 and compound 2 in the first embodiment of the present invention and second embodiment
Figure.
Fig. 3 is the structural schematic diagram of the electroluminescent device of the embodiment of the present invention.
Specific embodiment
For above content of the invention can be clearer and more comprehensible, preferred embodiment is cited below particularly, and institute's accompanying drawings is cooperated to make
It is described in detail.
The embodiment of the invention provides a kind of dark red photo-thermal to activate delayed fluorescence (thermally activated
Delayed fluorescence, TADF) material by cleverly MOLECULE DESIGN synthesized a series of depth of receptors containing quinones
Feux rouges thermal activation delayed fluorescence molecule.And this kind of molecular receptor contains carbonyl structure, so that molecule has high intersystem crossing speed
Rate constant and anti-intersystem crossing rate constant can effectively inhibit the reduction of the radiation transistion rate as caused by energy gap rule,
To obtain high photoluminescence quantum yield (photoluminescence quantum yield, PLQY).Pass through tune simultaneously
Position of the carbonyl in linear aromatic structure is saved, is improved to highest occupied molecular orbital (the highest occupied of receptor
Molecular orbital, HOMO) and minimum molecular orbital (lowest unoccupied molecular is not accounted for
Orbital, LUMO) overlapping degree, be capable of effectively suppression device efficiency roll-off, thus improve TADF molecule device effect
Rate prepares a series of high performance dark red smooth TADF organic light emissions using these luminescent materials provided by the embodiment of the present invention
Diode (OLED).
To achieve the above object, the embodiment of the invention provides a kind of dark red photo-thermal to activate delayed fluorescence (TADF) material,
Including the compound as composed by receptor A and donor D, the compound has general structure as shown in Equation 1:
D-A formula 1
Wherein the receptor A is to select from following structural any one:
And
The donor D is to select from following structural any one:
Referring to Fig. 1, Fig. 1 is that the dark red photo-thermal of the embodiment of the present invention activates the preparation method of delayed fluorescence (TADF) material
Flow chart.As shown in Figure 1, the embodiment of the invention also provides a kind of preparations of dark red photo-thermal activation delayed fluorescence (TADF) material
Method includes the following steps:
Step S10, compound A-X and compound D-B (OH) 2 is added in the solution containing alkali, wherein the X is halogen,
The A is with any one in following structural:
The D is with any one in following structural:
Step S20, under an inert gas, palladium catalyst is added in Xiang Suoshu solution, reacts the first duration at the first temperature
To obtain a reaction solution；
Step S30, the reaction solution is cooled to second temperature, obtains a mixture；And
Step S40, isolate described dark red photo-thermal activation delayed fluorescence (TADF) material from the mixture, including by by
Compound composed by body A and donor D, the compound have general structure as shown in Equation 1:
D-A formula 1.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, first temperature is 55 DEG C to 65 DEG C, and described first when is 12 hours to 36 hours a length of.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, the second temperature is room temperature.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, in the step S10, the solution is toluene, the alkali is potassium carbonate and the palladium catalyst is four triphenyl phosphorus
Palladium.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, the step S30, which is further included, passes through extraction, washing, dehydration, filtering and centrifugal drying processing for the reaction solution to obtain
To the mixture.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, step S40 system is separated using col-umn chromatography, and leacheate used by the col-umn chromatography is volume ratio 1:1's
Petroleum ether: methylene chloride.
An embodiment according to the present invention, in the preparation method of described dark red photo-thermal activation delayed fluorescence (TADF) material
In, the compound A-X is 2- bromo aphthacene diketone or 2- bromo pentacene -5,7,12,14- tetrones, the compound D-B
(OH) 2 be 4- (diphenyl amino)-phenyl boric acid.
Embodiment 1
In specific embodiments of the present invention 1, the dark red photo-thermal of the target to be synthesized activates delayed fluorescence (TADF) material packet
Include the compound 1 of following structural 2:
Shown in the synthetic route following reaction formula 1 of the compound 1 of structural formula 2:
The detailed synthesis step of compound 1 is as follows:
By 2- bromo aphthacene -5,12- diketone (3.36g, 10mmol), 4- (diphenyl amino)-phenyl boric acid (3.18g,
11mmol), the 2.5M wet chemical of 30mL toluene and 10mL are added in Schlenk (Schlenk) bottle of 100mL, use argon
Gas carries out substituting gas.Then four triphenyl phosphorus palladiums (0.48g, 0.4mmol) are added, 80 DEG C of back flow reactions are for 24 hours.It is cooled to room temperature
Afterwards, reaction solution is extracted three times with DCM, three times, anhydrous sodium sulfate dries, filters, and is spin-dried for for washing.With 200-300 purpose
Silica gel carries out column chromatography, and leacheate is petroleum ether, and: DCM (1:1, V/V) obtains red solid 4.06g, yield 81%.HRMS[M+
H]+calcd.for C36H23NO2:501.1729；found:501.1743.
Embodiment 2
In specific embodiments of the present invention 2, the dark red photo-thermal of the target to be synthesized activates delayed fluorescence (TADF) material packet
Include the compound 2 of following structural 3:
Shown in the synthetic route following reaction formula 2 of the compound 2 of structural formula 3:
The detailed synthesis step of compound 2 is as follows:
By 2- bromo pentacene -5,7,12,14- tetrones (4.16g, 10mmol), 4- (diphenyl amino)-phenyl boric acid
The 2.5M wet chemical of (3.18g, 11mmol), 30mL toluene and 10mL are added to Schlenk (Schlenk) bottle of 100mL
In, it is carried out substituting gas with argon gas.Then four triphenyl phosphorus palladiums (0.48g, 0.4mmol) are added, 80 DEG C of back flow reactions are for 24 hours.It is cooling
To room temperature, reaction solution is extracted three times with DCM, three times, anhydrous sodium sulfate dries, filters, and is spin-dried for for washing.Use 200-
The silica gel of 300 mesh carries out column chromatography, and leacheate is petroleum ether, and: DCM (1:1, V/V) obtains red solid 4.76g, yield 82%.
HRMS[M+H]+calcd.for C40H23NO4:581.1627；found:581.1643.
Specifically, compound 1 and compound 2 are defined and are respectively provided with structure shown in formula 2, formula 3, to the compound 1 and
Compound 2 is tested, and the fluorescence emission spectrum of the compound 1 and compound 2 under pure film is as shown in Fig. 2, the chemical combination
Object 1 and compound 2 go out minimum singlet state (S10) and lowest triplet state energy level (T1) and photic based on B3LYP theoretical calculation
Photoluminescence quantum yield (PLQY) is as shown in table 1 below:
Table 1
| PL Peak(nm) | S10(eV) | T1(eV) | ΔEST(eV) | PLQY (%) | |
| Compound 1 | 645 | 2.33 | 2.19 | 0.14 | 83 |
| Compound 2 | 676 | 2.11 | 1.99 | 0.12 | 79 |
Wherein, PL peak is luminescence generated by light peak, and S10 is minimum singlet level, T1For lowest triplet state energy level, Δ EST
For the energy level difference of minimum singlet level and lowest triplet state energy level.
In conjunction with Fig. 2 and table 1 it is found that the performance of the compound 1 and compound 2 of the invention meets the requirements.
In addition, the embodiment of the present invention also provides a kind of electroluminescent device, it is glimmering including above-mentioned dark red photo-thermal activation delay
Light (TADF) material.
Referring to Fig. 3, specifically, the electroluminescent device 100 includes basal layer 1；Hole injection layer 2 is located at institute
It states on basal layer 1；Hole transmission layer 3 is located on the hole injection layer 2；Luminescent layer 4 is located on the hole transmission layer 3；
Electron transfer layer 5 is located on the luminescent layer 4；And cathode layer 6, it is located on the electron transfer layer 5, wherein described shine
Layer 4 includes that dark red photo-thermal provided by the present invention activates delayed fluorescence (TADF) material.
An embodiment according to the present invention, in the electroluminescent device, the material of the basal layer 1 includes ITO；Institute
The material for stating hole injection layer 2 includes six cyano -1,4,5,8,9,12- of 2,3,6,7,10,11-, six azepine benzophenanthrene (HATCN)；
The material of the hole transmission layer 3 includes 4,4'- cyclohexyl two [N, N- bis- (4- aminomethyl phenyl) aniline] (TAPC)；The electronics
The material of transport layer 5 includes 1,3,5- tri- (3- (3- pyridyl group) phenyl) benzene (Tm3PyPB)；And the material of the cathode layer 6
Including lithium fluoride and aluminium.
Specifically, compound 1 is respectively adopted and compound 2 is used as 4 making devices 100 of luminescent layer and device 200, and to institute
It states device 100 and 200 progressive of device can be carried out measurement.Wherein, basal layer 1 and institute described in the device 100 and device 200
Hole injection layer 2 is stated with a thickness of 30nm.The hole transmission layer 3 with a thickness of 40nm.The luminescent layer 4 of the device 100 includes
5% compound 1, with a thickness of 40nm；The luminescent layer 4 of the device 200 includes 5% compound 2, with a thickness of 40nm.Electron-transport
Layer 5 with a thickness of 40nm.Lithium fluoride in cathode 500 with a thickness of 1nm, aluminium with a thickness of 100nm.
Current versus brightness-the voltage characteristic for further measuring the device 100 and the device 200, by with corrected
The source Keithley measuring system (Keithley 2400Sourcemeter, Keithley of silicon photoelectric diode
It 2000Currentmeter) is completed, electroluminescent spectrum is by French JY company SPEX CCD3000 spectrometer measurement, institute
There is measurement to complete in atmosphere at room temperature.The performance of the device 100 and device 200 that measure is as shown in table 2, it is known that device 100 and
The performance of device 200 meets the requirements.
Table 2
Accordingly, the embodiment of the invention provides a kind of dark red photo-thermal to activate delayed fluorescence (TADF) material, by cleverly
MOLECULE DESIGN has synthesized a series of dark red photo-thermal activation delayed fluorescence molecule of receptors containing quinones.And this kind of molecular receptor contains
Carbonyl structure so that molecule have high intersystem crossing rate constant and anti-intersystem crossing rate constant, can effectively inhibit by
The reduction of the radiation transistion rate caused by energy gap rule, to obtain high PLQY.Simultaneously by adjusting carbonyl in linear virtue
Position in fragrant structure is improved to the overlapping degree of the HOMO and LUMO of receptor, and the efficiency roll-off of effective suppression device is capable of, from
And the device efficiency of TADF molecule is improved, a series of high performance depths are prepared using these luminescent materials provided by the present invention
Feux rouges TADF Organic Light Emitting Diode (OLED).
In conclusion although the present invention has been disclosed above in the preferred embodiment, but above preferred embodiment is not to limit
The system present invention, those skilled in the art can make various changes and profit without departing from the spirit and scope of the present invention
Decorations, therefore protection scope of the present invention subjects to the scope of the claims.
Claims (10)
1. a kind of dark red photo-thermal activates delayed fluorescence material, including the compound as composed by receptor A and donor D, the chemical combination
Object has general structure as shown in Equation 1:
D-A formula 1
Wherein the receptor A is to select from following structural any one:
And
The donor D is to select from following structural any one:
2. a kind of preparation method of dark red photo-thermal activation delayed fluorescence material, includes the following steps:
Step S10, compound A-X and compound D-B (OH) is added in the solution containing alkali2, wherein the X is halogen, the A
For with any one in following structural:
The D is with any one in following structural:
Step S20, under an inert gas, palladium catalyst is added in the solution to described containing alkali, when reacting first at the first temperature
Length is to obtain reaction solution；
Step S30, the reaction solution is cooled to second temperature, obtains mixture；And
Step S40, the dark red photo-thermal activation delayed fluorescence material is isolated from the mixture, including by receptor A and donor D
Composed compound, the compound have general structure as shown in Equation 1:
D-A formula 1.
3. the preparation method of dark red photo-thermal activation delayed fluorescence material as claimed in claim 2, wherein first temperature is
55 DEG C to 65 DEG C, described first when, is 12 hours to 36 hours a length of.
4. the preparation method of dark red photo-thermal activation delayed fluorescence material as claimed in claim 2, wherein the second temperature is
Room temperature.
5. the preparation method of dark red photo-thermal activation delayed fluorescence material as claimed in claim 2, wherein in the step S10,
The solution containing alkali is toluene, the alkali is potassium carbonate and the palladium catalyst is four triphenyl phosphorus palladiums.
6. the preparation method of dark red photo-thermal activation delayed fluorescence material as claimed in claim 2, wherein the step S30 is more
Including handling the reaction solution by extraction, washing, dehydration, filtering and centrifugal drying to obtain the mixture.
7. the preparation method of dark red photo-thermal activation delayed fluorescence material as claimed in claim 2, wherein step S40 system
It is separated using col-umn chromatography, leacheate used by the col-umn chromatography is the petroleum ether of volume ratio 1:1: methylene chloride.
8. the preparation method of dark red photo-thermal activation delayed fluorescence material as claimed in claim 2, wherein the compound A-X is
2- bromo aphthacene diketone or 2- bromo pentacene -5,7,12,14- tetrones, the compound D-B (OH)2For 4- (diphenyl ammonia
Base)-phenyl boric acid.
9. a kind of electroluminescent device, comprising:
Basal layer；
Hole injection layer is located on the basal layer；
Hole transmission layer is located on the hole injection layer；
Luminescent layer is located on the hole transmission layer；
Electron transfer layer is located on the luminescent layer；And
Cathode layer is located on the electron transfer layer,
Wherein the luminescent layer includes that dark red photo-thermal as described in claim 1 activates delayed fluorescence material.
10. electroluminescent device as claimed in claim 9, wherein
The material of the basal layer includes ITO；
The material of the hole injection layer includes six cyano -1,4,5,8,9,12- of 2,3,6,7,10,11-, six azepine benzophenanthrene；
The material of the hole transmission layer includes 4,4'- cyclohexyl two [N, N- bis- (4- aminomethyl phenyl) aniline]；
The material of the electron transfer layer includes 1,3,5- tri- (3- (3- pyridyl group) phenyl) benzene；And
The material of the cathode layer includes lithium fluoride and aluminium.
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| PCT/CN2019/086363 WO2020215388A1 (en) | 2019-04-23 | 2019-05-10 | Deep red light thermally activated delayed fluorescence material, preparation method therefor, and electroluminescent device |
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| CN107987256B (en) * | 2017-12-07 | 2020-01-31 | 中国科学院长春应用化学研究所 | red heat-induced delayed fluorescence polymer and preparation and application thereof |
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