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 PDF

Info

Publication number
CN110240550A
CN110240550A CN201910534436.1A CN201910534436A CN110240550A CN 110240550 A CN110240550 A CN 110240550A CN 201910534436 A CN201910534436 A CN 201910534436A CN 110240550 A CN110240550 A CN 110240550A
Authority
CN
China
Prior art keywords
electron
delayed fluorescence
activation delayed
thermal activation
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910534436.1A
Other languages
Chinese (zh)
Other versions
CN110240550B (en
Inventor
罗佳佳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
Original Assignee
Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd filed Critical Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
Priority to CN201910534436.1A priority Critical patent/CN110240550B/en
Publication of CN110240550A publication Critical patent/CN110240550A/en
Application granted granted Critical
Publication of CN110240550B publication Critical patent/CN110240550B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C255/47—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of rings being part of condensed ring systems
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

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

A kind of thermal activation delayed fluorescence material, preparation method and electroluminescent device
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.
CN201910534436.1A 2019-06-20 2019-06-20 Thermal activation delayed fluorescent material, preparation method and electroluminescent device Active CN110240550B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910534436.1A CN110240550B (en) 2019-06-20 2019-06-20 Thermal activation delayed fluorescent material, preparation method and electroluminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910534436.1A CN110240550B (en) 2019-06-20 2019-06-20 Thermal activation delayed fluorescent material, preparation method and electroluminescent device

Publications (2)

Publication Number Publication Date
CN110240550A true CN110240550A (en) 2019-09-17
CN110240550B CN110240550B (en) 2022-04-26

Family

ID=67888363

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910534436.1A Active CN110240550B (en) 2019-06-20 2019-06-20 Thermal activation delayed fluorescent material, preparation method and electroluminescent device

Country Status (1)

Country Link
CN (1) CN110240550B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110563633A (en) * 2019-08-30 2019-12-13 武汉华星光电半导体显示技术有限公司 Blue light thermal activation delay fluorescent material, preparation method thereof and electroluminescent device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101684095A (en) * 2008-06-24 2010-03-31 葛来西雅帝史派有限公司 Novel organic electroluminescent compounds and organic electroluminescent device using the same
DE102015112501A1 (en) * 2015-07-30 2017-02-02 Rafal Czerwieniec Organic molecules with two non-conjugated bridges between donor and acceptor for effective thermally activated delayed fluorescence for use in opto-electronic devices
CN107109212A (en) * 2014-11-18 2017-08-29 国立研究开发法人科学技术振兴机构 Power mutagens color luminescent material, make the power mutagens color luminescent material be crosslinked obtained by power mutagens chromoresin and the manufacture method of the two
CN109369652A (en) * 2018-11-15 2019-02-22 武汉华星光电半导体显示技术有限公司 A kind of blue light thermal activation delayed fluorescence material and its application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101684095A (en) * 2008-06-24 2010-03-31 葛来西雅帝史派有限公司 Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN107109212A (en) * 2014-11-18 2017-08-29 国立研究开发法人科学技术振兴机构 Power mutagens color luminescent material, make the power mutagens color luminescent material be crosslinked obtained by power mutagens chromoresin and the manufacture method of the two
DE102015112501A1 (en) * 2015-07-30 2017-02-02 Rafal Czerwieniec Organic molecules with two non-conjugated bridges between donor and acceptor for effective thermally activated delayed fluorescence for use in opto-electronic devices
CN109369652A (en) * 2018-11-15 2019-02-22 武汉华星光电半导体显示技术有限公司 A kind of blue light thermal activation delayed fluorescence material and its application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王士攀: "二氰基取代芳香共轭基团为受体构建热活化延迟荧光材料体系", 《中国博士学位论文全文数据库》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110563633A (en) * 2019-08-30 2019-12-13 武汉华星光电半导体显示技术有限公司 Blue light thermal activation delay fluorescent material, preparation method thereof and electroluminescent device
CN110563633B (en) * 2019-08-30 2022-11-08 武汉华星光电半导体显示技术有限公司 Blue-light thermal activation delay fluorescent material, preparation method thereof and electroluminescent device

Also Published As

Publication number Publication date
CN110240550B (en) 2022-04-26

Similar Documents

Publication Publication Date Title
CN102031104B (en) Bipolar phosphorescent main material containing anthracene derivatives of tetraphenyl silicane and carbazole and organic electroluminescent device
CN109456276A (en) Dark red photo-thermal activation delayed fluorescence material and its synthetic method, electroluminescent device
WO2020082600A1 (en) Near-infrared photothermal activation delayed fluorescent material and preparation method therefor, and display device
WO2020211122A1 (en) Bipolar thermally activated delayed fluorescence material, preparation method therefor, and organic electroluminescent diode device
CN111747932B (en) Compound, application thereof and organic electroluminescent device
CN104497013A (en) Aza carbazole OLED (organic light emitting diode) material as well as preparation method and application thereof
CN114163424A (en) Organic electroluminescent material and device thereof
CN109503508A (en) Green light thermal activation delayed fluorescence material and its synthetic method, electroluminescent device
WO2020211125A1 (en) Thermally-activated delayed fluorescent material and preparation method therefor, and organic light-emitting diode device
CN115073501A (en) Organic electroluminescent material and device thereof
CN110183426B (en) Thermal activation delayed fluorescent material, preparation method and electroluminescent device
CN110143960A (en) Green light thermal activation delayed fluorescence material and preparation method thereof, organic electroluminescence device
CN114249738A (en) Electroluminescent material and device
WO2021120450A1 (en) Thermally-activated delayed fluorescence green light polymer material and preparation method therefor
CN113968873A (en) Organic electroluminescent material and device thereof
CN110240550A (en) A kind of thermal activation delayed fluorescence material, preparation method and electroluminescent device
CN110256475A (en) Dark blue photo-thermal activation delayed fluorescence material and preparation method thereof and electroluminescent device
CN117327056A (en) Organic electroluminescent material and device thereof
CN110563633A (en) Blue light thermal activation delay fluorescent material, preparation method thereof and electroluminescent device
CN110015994A (en) Thermal activation delayed fluorescence material and preparation method thereof, display device
CN109678851A (en) Hot activation delayed fluorescence material, organic electroluminescence device and display panel
CN113429397B (en) Compound, display panel and display device
CN114181235A (en) Polycyclic compounds and devices thereof
CN109721588A (en) Organic electroluminescence device compound and the organic electroluminescence device for using it
CN114256430A (en) Electroluminescent device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant