CN110240550A - A kind of thermal activation delayed fluorescence material, preparation method and electroluminescent device - Google Patents
A kind of thermal activation delayed fluorescence material, preparation method and electroluminescent device Download PDFInfo
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Abstract
The present invention provides a kind of improved thermal activation delayed fluorescence materials, preparation method and fluorescent device, electron donor in fluorescent material is connected with electron acceptor by dibenzo octatomic ring, replace with electron-withdrawing group F and cyano, reconnect different electron units, it is a series of poor with lower single triplet to have synthesized, high-luminous-efficiency, the quickly blue light thermal activation delayed fluorescence material of reversed intersystem crossing constant, the structure for realizing electron unit simultaneously is finely tuned so that spectrum is finely tuned, realize ultrafast reversed intersystem crossing rate, the synthesis of the TADF material of high-luminous-efficiency and its application in luminescent device.
Description
Technical field
The present invention relates to field of photoelectric technology, more particularly to a kind of thermal activation delayed fluorescence material, preparation method and electricity
Electroluminescence device.
Background technique
Organic electroluminescent LED (organic light-emitting diodes, OLEDs) has and actively sends out
Light does not need that backlight, luminous efficiency are high, visible angle is big, fast response time, Acclimation temperature range are big, production and processing technology phase
The advantages that simple, driving voltage is low, energy consumption is small, lighter and thinner, Flexible Displays and huge application prospect, have attracted crowd
The concern of more researchers.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 is fluorescent material, due to swashing for the singlet state in OLED and triplet
Sub- ratio is 1:3, and therefore, the theoretical internal quantum efficiency (IQE) of the OLED based on fluorescent material can only achieve 25%, is greatly limited
The application of fluorescence electroluminescent device is made.Heavy metal complex phosphor material due to heavy atom Effect of Spin-orbit Coupling,
Allow it to realize 100% IQE using singlet state and triplet exciton simultaneously.However, usually used heavy metal is all
It is the precious metals such as Ir, Pt, and heavy metal complex phosphorescent light-emitting materials still need to be broken through in terms of blue light material.It is pure organic
Thermal activation delayed fluorescence (TADF) material, by cleverly MOLECULE DESIGN, so that molecule has the lesser minimum triple energy levels of list
Poor (Δ EST), such triplet exciton can return to singlet state by reversed intersystem crossing (RISC), then extremely by radiation transistion
Ground state and shine, so as to which using single, triplet exciton, 100% IQE also may be implemented simultaneously.
For TADF material, quick reversed intersystem crossing constant (kRISC) and high photoluminescence quantum yield
It (PLQY) is the necessary condition for preparing high efficiency OLED.Currently, the TADF material for having above-mentioned condition is matched relative to heavy metal Ir
It is still deficienter for conjunction object.
The present invention replaces in view of the above-mentioned problems, in the structure basis of eight ring of dibenzo with electron-withdrawing group F and cyano,
Different electron units is reconnected, it is a series of poor with lower single triplet to have synthesized, and high-luminous-efficiency is quickly anti-
To the blue light thermal activation delayed fluorescence material of intersystem crossing constant, while the structure for realizing electron unit is finely tuned so that spectrum
Fine tuning.Confirmed by structure of the mass spectral analysis to them, then their Photophysics be studied in detail,
These blue lights TADF material is applied to luminescent layer and is prepared for a series of high performance OLED by last base.
Summary of the invention
In order to solve the above technical problems, the present invention provides improved thermal activation delayed fluorescence material, in eight ring of dibenzo
Structure basis on, replace with electron-withdrawing group F and cyano, reconnect different electron units, having synthesized a series of has
Lower list triplet is poor, high-luminous-efficiency, quickly the blue light thermal activation delayed fluorescence material of reversed intersystem crossing constant,
Meanwhile the structure for realizing electron unit is finely tuned so that spectrum is finely tuned.
The present invention provides a kind of thermal activation delayed fluorescence materials, are mutually tied by electron donor (D) with electron acceptor (A)
It closes, in which: the general structure of the fluorescent material are as follows:
Electron donor and electron acceptor in the fluorescent material pass through dibenzo octatomic ring
Connection, electron acceptor (A) are(5E, 11E) -2,3,8,9- tetrafluoro hexichol { a, e } { 8 } annulene -5,11-
Dintrile), the electron donor (D) is diphenylaminesCarbazolePhenoxazineIn optionally
It is a kind of.
It is center core that the general character of general structure of the invention, which is with hexichol { a, e } { 8 } annulene, adds fluorine and cyano to increase
Its electron-withdrawing ability forms electron acceptor, in R1And R2Position connects different electron acceptors and carries out permutation and combination, shares 72 kinds
The compound of different structure.
The structure of the fluorescent material can be selected from choosing any one kind of them in following three kinds of compounds:
The R1And R2It can be selected from choosing any one kind of them in following monomeric groups:
A kind of electroluminescent device of the present invention, uses hot activation delayed fluorescence material as luminescent layer, in which: including according to
It is secondary to be stacked: substrate layer, hole injection layer, transport layer, luminescent layer, electron transfer layer and cathode layer;
The substrate layer is the glass that there is tin indium oxide on surface layer, and the tin indium oxide is anode;
The hole injection layer is used for the hole transport to the luminescent layer;
The transport layer, the transmission for carrier hole and electronics;
The cathode layer is for providing electronics;
The electron transfer layer is used for the electron-transport to the luminescent layer;
The luminescent layer includes hot activation delayed fluorescence material as described in claim 1, and the luminescent layer is used for institute
Hole and the compound generation exciton of electronics are stated, the hot activation delayed fluorescence material is made to shine under the action of exciton.
The present invention also provides a kind of methods for preparing thermal activation delayed fluorescence material comprising following steps:
Step 1) is proportionally added into raw material: electron donor, electron acceptor and solvent are mutually mixed;
Catalyst sodium tert-butoxide (NaOt-Bu) is added in step 2), and the toluene of water removal deoxygenation is added under argon atmosphere, adds
It thermal response 20-24 hours, is cooled to room temperature;
Step 3) pours into reaction solution in ice water, and methylene chloride extracts three times, merges organic phase, revolves into silica gel;
Step 4) column chromatographic isolation and purification, obtains light blue powder.
The raw material includes electron donor and electron acceptor, in which: electron acceptor (A) is(5E,
11E) -2,3,8,9- tetrafluoro hexichol { a, e } { 8 } annulene -5,11- dintrile), the electron donor (D) is diphenylaminesCarbazolePhenoxazineIn choose any one kind of them.
The solvent further includes palladium acetate and tri-tert-butylphosphine tetrafluoroborate.
The investment of the electron donor matches are as follows: 2.41g, concentration 5mmol/L, the investment proportion of the electron acceptor:
2.0-2.2g, concentration 12mmol/L, the investment proportion of the palladium acetate are as follows: 90mg, concentration 0.4mmol/L, three uncle
The investment proportion of butyl phosphine tetrafluoroborate is 0.34g, concentration 1.2mmol/L.
Compared with prior art, the present invention provides a kind of improved thermal activation delayed fluorescence material, pass through different function
The collocation of group, is connected by dibenzo octatomic ring, is regulated and controled to the structure of donor monomer, change its electron donation,
The effective luminous efficiency for increasing material, at the same time, studying the strong and weak of charge transfer state influences material property bring, base
Very high efficiency is all achieved in the electroluminescent device of target blue light TADF material.Improved thermal activation delayed fluorescence is provided
The purpose of material be realize ultrafast reversed intersystem crossing rate, high-luminous-efficiency TADF material synthesis and its in photophore
Application in part.Confirmed by structure of the mass spectral analysis to them, then their Photophysics have been carried out in detail
Research, these blue lights TADF material is applied to luminescent layer and is prepared for a series of high performance OLED by last base.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of electroluminescent device of the present invention.
Specific embodiment
In OLED display screen field, general TADF material has the molecule that combines of electron donor (D) and electron acceptor (A)
Structure, the present invention are regulated and controled by the structure to electron donor unit, change its electron donation, effectively to increase material
The luminous efficiency of material, and material property is promoted by the strong and weak of charge transfer state.Meanwhile applying in blue light TADF material, it mentions
Rise the luminous efficiency of electroluminescent device.
The purpose of the present invention, be realize ultrafast reversed intersystem crossing rate, high-luminous-efficiency TADF material synthesis with
And its application in luminescent device.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of thermal activation delayed fluorescence materials, by electron donor
(D) it is combined with electron acceptor (A), in which: the general structure of the fluorescent material are as follows:
Electron donor and electron acceptor in the fluorescent material pass through dibenzo octatomic ring
Connection, electron acceptor (A) are(5E, 11E) -2,3,8,9- tetrafluoro hexichol { a, e } { 8 } annulene -5,11- two
Nitrile), the electron donor (D) is diphenylaminesCarbazolePhenoxazineIn optional one
Kind.It is center core that the general character of general structure of the invention, which is with hexichol { a, e } { 8 } annulene, adds fluorine and cyano to increase its suction
Electronic capability forms electron acceptor, in R1And R2Position connects different electron acceptors and carries out permutation and combination, shares 72 kinds of differences
The compound of structure is reacted by the way that different electron acceptor is added and is combined with electron donor, in difference to replacing in electric position
It changes, obtains the fluorescent material of different structure formula.
Wherein, the R1And R2It can be selected from choosing any one kind of them in following monomeric groups:
It is reacted to each other the structural formula of the fluorescent material of acquisition, be can be selected from following by electron donor (D) and electron acceptor (A)
It chooses any one kind of them in three kinds of compounds:
The present invention also provides a kind of methods for preparing thermal activation delayed fluorescence material comprising following steps:
Step 1) is proportionally added into raw material: electron donor, electron acceptor and solvent are mutually mixed;
Catalyst n aOt-Bu (sodium tert-butoxide) is added in step 2), and the toluene of water removal deoxygenation is added under argon atmosphere, adds
It thermal response 20-24 hours, is cooled to room temperature;
Step 3) pours into reaction solution in ice water, and methylene chloride extracts three times, merges organic phase, revolves into silica gel, and remove
Water-solubility impurity in reactant;
Step 4) column chromatographic isolation and purification, obtains light blue powder.
Preferably, the raw material includes electron donor and electron acceptor, in which: electron acceptor (A) is(5E, 11E) -2,3,8,9- tetrafluoro hexichol { a, e } { 8 } annulene -5,11- dintrile), the electron donor
It (D) is diphenylaminesCarbazolePhenoxazineIn choose any one kind of them.
Solvent is palladium acetate (Pd (OAc)2) and tri-tert-butylphosphine tetrafluoroborate ((t-Bu)3HPBF4)。
Preferably, in step 2), the toluene of water removal deoxygenation is added under argon atmosphere, is reacted 24 hours at 120 DEG C, it is cooling
To room temperature;
Preferably, the investment proportion of the electron donor are as follows: 2.41g, concentration 5mmol/L, the throwing of the electron acceptor
Enter proportion: 2.0-2.2g, concentration 12mmol/L, the investment proportion of the palladium acetate are as follows: 90mg, concentration 0.4mmol/L, institute
The investment proportion for stating tri-tert-butylphosphine tetrafluoroborate is 0.34g, concentration 1.2mmol/L.
Preferably, in step 4), methylene chloride and n-hexane is added and carries out column chromatographic isolation and purification, methylene chloride and just oneself
The proportion (volume ratio) of alkane is 1:2, by column chromatographic isolation and purification, obtains light blue powder, i.e., with the blue light of TADF characteristic
Thermal activation delayed fluorescence material.
The synthetic method and synthetic reaction of the fluorescent material of three kinds of structural formulas are illustrated individually below.
Embodiment one
Fluorescent material compound 1 is synthesized, synthetic route is as follows:
Electron acceptor (A) raw material 1 is added into bis- mouthfuls of bottles of 100mL(proportion 2.41g, concentration
5mmol), electron donor (D) diphenylamines(proportion 2.03g, concentration 12mmol), palladium acetate (Pd (OAc)2) (match
Than 90mg, concentration 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate ((t-Bu)3HPBF4) (proportion 0.34g, concentration
1.2mmol);Then, NaOt-Bu (proportion 1.16g, concentration 12mmol) is added in glove box, under argon atmosphere, squeezes into
60mL removes water the toluene of deoxygenation in advance, reacts 24 hours, is cooled to room temperature at 120 DEG C;Then, reaction solution is poured into 200mL ice
In water, methylene chloride is extracted three times, merges organic phase, is revolved into silica gel;Methylene chloride is added and n-hexane carries out column chromatography for separation
The proportion (volume ratio) of purifying, methylene chloride and n-hexane is 1:2, by column chromatographic isolation and purification, obtains light blue powder
1.6g i.e. compound 1Yield 48%.Mass spectral analysis MS (EI) m/z:660.10.Show to obtain
Product as the structure that we design.
Embodiment two
Fluorescent material compound 2 is synthesized, synthetic route is as follows:
Electron acceptor (A) raw material 1 is added into bis- mouthfuls of bottles of 100mL(proportion 2.41g, concentration
5mmol), electron donor (D) carbazole(proportion 2.00g, concentration 12mmol), palladium acetate ((Pd (OAc)2) (proportion
90mg, concentration 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate ((t-Bu)3HPBF4) (proportion 0.34g, concentration 1.2mmol),
Then, NaOt-Bu (proportion 1.16g, concentration 12mmol) is added in glove box, under argon atmosphere, squeezes into 60mL and removes in advance
The toluene of water deoxygenation is reacted 24 hours at 120 DEG C, is cooled to room temperature;Reaction solution is poured into 200mL ice water, methylene chloride extraction
It takes three times, merges organic phase, revolve into silica gel;Methylene chloride and n-hexane is added and carries out column chromatographic isolation and purification, methylene chloride and
The proportion (volume ratio) of n-hexane is 1:2, by column chromatographic isolation and purification, obtains light blue powder 1.4g, i.e. compound 2Yield 43%.Mass spectral analysis MS (EI) m/z:656.11.
Embodiment three
Fluorescent material compound 3 is synthesized, synthetic route is as follows:
Electron acceptor (A) raw material 1 is added into bis- mouthfuls of bottles of 100mL(proportion 2.41g, concentration
5mmol), electron donor (D) phenoxazine(proportion 2.2g, concentration 12mmol), palladium acetate ((Pd (OAc)2) (match
Than 90mg, concentration 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate ((t-Bu)3HPBF4) (proportion 0.34g, concentration
1.2mmol), then, NaOt-Bu (proportion 1.16g, concentration 12mmol) is added in glove box, under argon atmosphere, squeezes into
60mL removes water the toluene of deoxygenation in advance, reacts 24 hours, is cooled to room temperature at 120 DEG C;Reaction solution is poured into 200mL ice water,
Methylene chloride extracts three times, merges organic phase, revolves into silica gel;Methylene chloride is added and n-hexane carries out column chromatographic isolation and purification,
The proportion (volume ratio) of methylene chloride and n-hexane is 1:2, by column chromatographic isolation and purification, obtains light blue powder 1.9g, i.e.,
Compound 3Yield 55%.Mass spectral analysis MS (EI) m/z:688.08.
The theoretical modeling of the thermal activation delayed fluorescence material compound prepared calculates:
The minimum singlet state (S1) and lowest triplet state energy level (T1) of target molecule, electrochemistry energy level is as shown in table 1 below,
Target molecule | PL Peak(nm) | S1(eV) | T1(eV) | EST(eV) | HOMO(eV) | LUMO(eV) |
Compound 1 | 466 | 2.66 | 2.58 | 0.08 | -5.43 | -2.54 |
Compound 2 | 462 | 2.69 | 2.63 | 0.06 | -5.56 | -2.53 |
Compound 3 | 470 | 2.64 | 2.51 | 0.13 | -5.61 | -2.54 |
Shown in referring to Fig.1, the present invention also provides a kind of electroluminescent devices, and hot activation delayed fluorescence material is used to make
For luminescent layer, in which: including being cascading: substrate layer 1, hole injection layer 2, transmitting layer 3, luminescent layer 4, electron transfer layer
5 and cathode layer 6;Wherein,
The substrate layer is the glass that there is tin indium oxide on surface layer, and the tin indium oxide is anode;
The hole injection layer, for giving the hole transport to the luminescent layer, by MoO3It is made;
The transport layer, the transmission for carrier hole and electronics;
The cathode layer is made for providing electronics of lithium fluoride/aluminium;
The electron transfer layer is used for the electron-transport to the luminescent layer, by 1,3,5- tri- (3- (3- pyridyl group)
Phenyl) benzene Tm3PyPB is made;
The luminescent layer includes hot activation delayed fluorescence material, and the luminescent layer is used for the hole and the compound production of electronics
Raw exciton, makes the hot activation delayed fluorescence material shine under the action of exciton.
Electroluminescent device can be made by means known in the art, such as by bibliography (Adv.Mater.2003,15,
277.) production of method disclosed in.Method particularly includes: on electro-conductive glass (ITO) substrate through over cleaning, under high vacuum condition according to
Secondary vapor deposition hole injection layer MoO3, transport layer TCTA, luminescent layer DPEPO+ thermal activation delayed fluorescence material, electron transfer layer
The Al of the LiF and 100nm of Tm3PyPB, 1nm.Device as shown in Figure 1 is made with this method, various specific device architectures are such as
Under:
1 (A of device1):
ITO/MoO3(2nm)/TCTA (35nm)/DPEPO: compound 1 (8%20nm)/Tm3PyPB(40nm)/LiF
(1nm)/Al(100nm)
2 (A of device2):
ITO/MoO3(2nm)/TCTA (35nm)/DPEPO: compound 2 (8%20nm)/Tm3PyPB(40nm)/LiF
(1nm)/Al(100nm)
3 (A of device3):
ITO/MoO3(2nm)/TCTA (35nm)/DPEPO: compound 3 (8%20nm)/Tm3PyPB(40nm)/LiF
(1nm)/Al(100nm)
Current versus brightness-voltage characteristic of device is measured by the source Keithley with corrected silicon photoelectric diode
What system (Keithley 2400Sourcemeter, Keithley 2000Currentmeter) was completed, electroluminescent spectrum is
By French JY company SPEX CCD3000 spectrometer measurement, all measurements are completed in atmosphere at room temperature.
The performance data of device see the table below:
Device | Maximum current efficiency (cd/A) | EL peak(nm) | Maximum external quantum efficiency (%) |
Device 1 | 37.9 | 471 | 18.9 |
Device 2 | 35.1 | 468 | 16.7 |
Device 3 | 39.6 | 479 | 19.8 |
Above-mentioned parameter illustrates that the device performance of material is high, and general blue phosphor, maximum external quantum efficiency is on 8% left side
The right side, and TADF material of the invention its maximum external quantum efficiency is 18%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications, these improvements and modifications can also be made
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of thermal activation delayed fluorescence material is combined, it is characterised in that: institute by electron donor (D) and electron acceptor (A)
State the general structure of fluorescent material are as follows:
Electron donor and electron acceptor in the fluorescent material are connected by dibenzo octatomic ring
It connects, electron acceptor (A) is(5E, 11E) -2,3,8,9- tetrafluoro hexichol { a, e } { 8 } annulene -5,11- two
Nitrile), the electron donor (D) is diphenylaminesCarbazolePhenoxazineIn optional one
Kind.
2. thermal activation delayed fluorescence material according to claim 1, it is characterised in that: the structure of the fluorescent material is optional
It chooses any one kind of them from following three kinds of compounds:
3. thermal activation delayed fluorescence material according to claim 1, it is characterised in that: the R1And R2It can be selected to place an order
It chooses any one kind of them in body group:
4. a kind of electroluminescent device uses hot activation delayed fluorescence material as luminescent layer, it is characterised in that: including successively
It is stacked: substrate layer, hole injection layer, transport layer, luminescent layer, electron transfer layer and cathode layer;
The substrate layer is the glass that there is tin indium oxide on surface layer, and the tin indium oxide is anode;
The hole injection layer is used for the hole transport to the luminescent layer;
The transport layer, the transmission for carrier hole and electronics;
The cathode layer is for providing electronics;
The electron transfer layer is used for the electron-transport to the luminescent layer;
The luminescent layer includes hot activation delayed fluorescence material as described in claim 1, and the luminescent layer is used for the sky
Cave and the compound generation exciton of electronics make the hot activation delayed fluorescence material shine under the action of exciton.
5. electroluminescent device according to claim 1, it is characterised in that: the luminescent layer includes thermal activation delayed fluorescence
Material is combined, the general structure of the fluorescent material by electron donor (D) and electron acceptor (A) are as follows:
Electron donor and electron acceptor in the fluorescent material are connected by dibenzo octatomic ring
It connects, electron acceptor (A) is(5E, 11E) -2,3,8,9- tetrafluoro hexichol { a, e } { 8 } annulene -5,11- two
Nitrile), the electron donor (D) is diphenylaminesCarbazolePhenoxazineIn optional one
Kind.
6. a kind of method for preparing thermal activation delayed fluorescence material, it is characterised in that the following steps are included:
Step 1) is proportionally added into raw material: electron donor, electron acceptor and solvent are mutually mixed;
Catalyst sodium tert-butoxide (NaOt-Bu) is added in step 2), and the toluene of water removal deoxygenation is added under argon atmosphere, and heating is anti-
It answers 20-24 hours, is cooled to room temperature;
Step 3) pours into reaction solution in ice water, and methylene chloride extracts three times, merges organic phase, revolves into silica gel;
Step 4) column chromatographic isolation and purification, obtains light blue powder.
7. preparing the method for thermal activation delayed fluorescence material according to claim 6, it is characterised in that: the raw material includes electricity
Sub- donor and electron acceptor, in which: the electron acceptor (A) is(5E, 11E) -2,3,8,9- tetrafluoro two
Benzene { a, e } { 8 } annulene -5,11- dintrile), the electron donor (D) is diphenylaminesCarbazolePheno
OxazinesIn choose any one kind of them.
8. preparing the method for thermal activation delayed fluorescence material according to claim 6, it is characterised in that: in step 2), in argon
Atmosphere encloses the lower toluene that water removal deoxygenation is added, and reacts 24 hours, is cooled to room temperature at 120 DEG C.
9. preparing the method for thermal activation delayed fluorescence material according to claim 7, it is characterised in that: the raw material further includes
Palladium acetate and tri-tert-butylphosphine tetrafluoroborate.
10. preparing the method for thermal activation delayed fluorescence material according to claim 9, it is characterised in that: the electron donor
Investment proportion are as follows: 2.41g, concentration 5mmol/L, the electron acceptor investment proportion: 2.0-2.2g, concentration are
12mmol/L, the investment proportion of the palladium acetate are as follows: 90mg, concentration 0.4mmol/L, the tri-tert-butylphosphine tetrafluoroborate
Investment proportion be 0.34g, concentration 1.2mmol/L.
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