WO2022052134A1 - 基于手性热激活延迟荧光材料的电致发光器件及其制备方法 - Google Patents

基于手性热激活延迟荧光材料的电致发光器件及其制备方法 Download PDF

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WO2022052134A1
WO2022052134A1 PCT/CN2020/115169 CN2020115169W WO2022052134A1 WO 2022052134 A1 WO2022052134 A1 WO 2022052134A1 CN 2020115169 W CN2020115169 W CN 2020115169W WO 2022052134 A1 WO2022052134 A1 WO 2022052134A1
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chiral
activated delayed
electroluminescent device
delayed fluorescent
fluorescent material
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PCT/CN2020/115169
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English (en)
French (fr)
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李艳青
谢凤鸣
唐建新
周经雄
曾馨逸
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苏州大学
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-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
    • 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]

Definitions

  • the invention relates to the field of organic electroluminescent materials, in particular to an electroluminescent device based on a chiral thermally activated delayed fluorescent material with good performance and industrialization and a preparation method thereof.
  • Electroluminescence (English electroluminescent), also known as electric field luminescence, or EL for short, is to generate an electric field through the voltage applied to the two electrodes, and the electrons excited by the electric field hit the luminescent center, causing electrons to transition, change, and A physical phenomenon in which recombination leads to luminescence. It is generally believed that under the action of a strong electric field, the energy of the electrons increases accordingly until it far exceeds the electron energy in the thermal equilibrium state and becomes superheated electrons. The superheated electrons can ionize the lattice through collisions during the movement to form electrons, empty electrons Hole pairs, when these ionized electron-hole pairs recombine or the excited luminescent centers return to the ground state, emit light.
  • Electroluminescence can be divided into high-field electroluminescence and low-field electroluminescence from the light-emitting principle.
  • High-field electroluminescence is an in vivo luminescence effect.
  • a light-emitting material is a semiconductor compound that is doped with appropriate impurities to introduce a light-emitting center or form a certain dielectric state. When it is in contact with an electrode or other medium, and its potential barrier is reversed, electrons from the electrode or interface state enter the high field region of the luminescent material, are accelerated and become superheated electrons.
  • Circularly polarized luminescence (CPL) has attracted extensive attention for its potential applications in 3D imaging, information storage, and quantum computing.
  • TADF organic light-emitting materials can theoretically achieve 100% internal quantum efficiency without precious metals, which has become a research hotspot.
  • CPL-TADF is mainly realized by grafting chiral small molecular fragments directly to the TADF molecular framework.
  • the invention discloses an electroluminescent device based on a chiral thermally activated delayed fluorescent material and a preparation method thereof.
  • the chemical name of the chiral thermally activated delayed fluorescent material is R/S-18,21-bis(10H-phenoxazine) -10-yl)-3,4,5,6,7,8,9,10-octahydrodibenzo[a,c]dinaphtho[2',1':5,6;1'', 2'': 7,8][1,4]dioxin[2,3-i]phenazine or R/S-16,17-bis(4-(10H-phenoxazin-10-yl)benzene base)-3,4,5,6,7,8,9,10-octahydrodinaphtho[2',1':5,6;1'',2'':7,8][1, 4] Dioxane[2,3-g]quinoxaline, to solve the problems of difficult synthesis and preparation
  • an electroluminescent device based on a chiral thermally activated delayed fluorescent material comprising a light-emitting layer doped with a chiral thermally activated delayed fluorescent material
  • the light-emitting layer of the electroluminescent device of the present invention comprises a hand A chiral thermally activated delayed fluorescent material, the chiral thermally activated delayed fluorescent material is used as a guest material and a host material is doped as a light-emitting layer; further, the doping concentration of the chiral thermally activated delayed fluorescent material is 2-20wt%, referring to The mass percentage of the chiral thermally activated delayed fluorescent material in the total amount of the light-emitting layer.
  • the electroluminescent device based on a chiral thermally activated delayed fluorescent material disclosed in the present invention is composed of an anode, a hole injection layer, a hole transport layer, a blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode; , indium tin oxide (ITO) was used as anode, bispyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-capronitrile (HATCN ) as a hole injection layer (HIL), 4,4'-(cyclohexane-1,1-diyl)bis(N,N-di-p-tolylaniline) (TAPC) as a hole transport layer (HTL), tris(4-(9H-carbazol-9-yl)phenyl)amine (TCTA) as electron/exciton blocking layer (EBL), the chiral thermally activated delayed fluorescent material as guest material do
  • the invention discloses a light-emitting layer for an electroluminescent device, which is a chiral thermally activated delayed fluorescent material doped with 4,4'-bis(9H-carbazol-9-yl)-1,1'-biphenyl.
  • the preparation method of the electroluminescent device based on the chiral thermally activated delayed fluorescent material is as follows: vacuum evaporation of a hole injection layer, a hole transport layer, a blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, A cathode is used to obtain the electroluminescent device based on the chiral thermally activated delayed fluorescent material. Vacuum evaporation is a conventional technique.
  • the chiral thermally activated delayed fluorescent material of the present invention is compound R-ODPPXZ, compound S-ODPPXZ, compound R-ODQPXZ or compound S-ODQPXZ, and the chemical structural formulas thereof are respectively as follows.
  • the preparation method of the above chiral orange-red photothermally activated delayed fluorescent material comprises the following steps: using 10,10'-(11,12-difluorodibenzo[a,c]phenazine-3,6-diyl ) bis(10H-phenoxazine), 5,5',6,6',7,7',8,8'-octahydrobinaphthol as raw materials, the chiral orange-red photothermal activation delay was prepared by reaction Fluorescent material compound R-ODPPXZ, compound S-ODPPXZ.
  • the molar ratio of ',7,7',8,8'-octahydrobinaphthol is 1:0.8 to 1.1; the reaction is carried out in the presence of a base and under nitrogen protection; the reaction temperature is 40 to 100 °C, and the reaction time for 12 to 24 hours.
  • the extraction solvent can be dichloromethane, chloroform, ethyl acetate, ice Either acetic acid or some combination of these solvents.
  • the preparation method of the above-mentioned chiral yellow photothermally activated delayed fluorescent material comprises the following steps: using 10,10'-(((6,7-difluoroquinoxaline-2,3-diyl)bis(4) ,1-phenylene)) bis(10H-phenoxazine), 5,5',6,6',7,7',8,8'-octahydrobinaphthol as raw materials, the reaction was prepared to obtain the Chiral yellow photothermal activated delayed fluorescent material compound R-ODQPXZ or compound S-ODQPXZ.
  • the molar ratio of 5',6,6',7,7',8,8'-octahydrobinaphthol is 1:0.8 ⁇ 1.1; the reaction is carried out in the presence of a base and under nitrogen protection; the reaction temperature is 40 ⁇ 100 ° C, the reaction time is 12 ⁇ 24 h.
  • reaction solution is extracted, then the organic phases are combined, and suction filtration is performed to obtain the chiral yellow light thermally activated delayed fluorescent material; Any one of methyl chloride, chloroform, ethyl acetate, glacial acetic acid or some combination of these solvents.
  • the invention provides a method for synthesizing and preparing a novel chiral thermally activated delayed fluorescent material; and an OLED based on the chiral thermally activated delayed fluorescent material, which achieves the goals of EQE exceeding 20% and asymmetry factor greater than 10 -3 ;
  • a novel chiral thermally activated delayed fluorescent material which achieves the goals of EQE exceeding 20% and asymmetry factor greater than 10 -3 ;
  • it solves the problems of many synthesis and preparation steps of the existing orange-red/red light TADF materials, expensive raw materials, and complicated synthesis and purification processes. , the yield is not high, and it is difficult to mass production.
  • the organic thin film formed by the invention has high surface smoothness, stable chemical and physical properties, high luminous efficiency and circularly polarized light properties, and the formed circularly polarized organic electroluminescent device has good performance.
  • R/S-18,21-bis(10H-phenoxazin-10-yl)-3,4,5,6,7,8,9,10-octa provided by the present invention Hydrodibenzo[a,c]dinaphtho[2',1':5,6; 1'',2'':7,8] [1,4]Dioxin[2,3-i]phenazine or R/S-16,17-bis(4-(10H-phenoxazin-10-yl)phenyl)-3,4,5 ,6,7,8,9,10-Octahydrodinaphtho[2',1':5,6;1'',2'':7,8][1,4]dioxane[2, 3-g]quinoxaline thermally activated delayed fluorescence material has the characteristics of rigid large planar twisted structure and remarkable internal charge transfer (ICT), with thermally activated delayed fluorescence (TADF) and circularly polarized
  • the CP-OLED device based on the chiral thermally activated delayed fluorescent material provided by the present invention has the advantages of low driving voltage and good luminous stability, and the external quantum efficiency EQE of the prepared circularly polarized device is as high as 28.3% and 20.3%, respectively. , the misalignment factor g is as high as 6 ⁇ 10 -4 and 2.4 ⁇ 10 -3 , respectively.
  • the chiral thermally activated delayed fluorescent material provided by the present invention has few synthesis and preparation steps, easy to obtain raw materials, simple synthesis and purification process, high yield, and can be synthesized and prepared on a large scale.
  • Organic electroluminescent devices based on it have good application prospects in the fields of lighting, flat panel display, sensing, night vision and biological imaging; circularly polarized light-emitting devices also have potential applications in 3D imaging, information storage, quantum computing, etc. application prospects.
  • FIG. 1 is the hydrogen nuclear magnetic spectrum of the compound R-ODPPXZ prepared in Example 1.
  • FIG. 2 is the carbon nuclear magnetic spectrum of the compound R-ODPPXZ prepared in Example 1.
  • FIG. 3 is the mass spectrum of the compound R-ODPPXZ prepared in Example 1.
  • FIG. 4 is the HPLC spectrum of the compound R-ODPPXZ prepared in Example 1.
  • FIG. 5 is the HPLC spectrum of the compound S-ODPPXZ prepared in Example 1.
  • FIG. 6 is the hydrogen nuclear magnetic spectrum of the compound R-ODQPXZ prepared in Example 2.
  • FIG. 8 is the mass spectrum of compound R-ODQPXZ prepared in Example 2.
  • FIG. 9 is the HPLC spectrum of compound R-ODQPXZ prepared in Example 2.
  • FIG. 10 is the HPLC spectrum of compound S-ODQPXZ prepared in Example 2.
  • FIG. 11 is the circular dichroism spectrum of the compounds prepared in Examples 1 and 2.
  • FIG. 11 is the circular dichroism spectrum of the compounds prepared in Examples 1 and 2.
  • FIG. 13 is a device performance diagram of application examples one and two.
  • FIG. 14 is a device efficiency diagram of the application example (1).
  • FIG. 15 is a device efficiency diagram of the application example (2).
  • Figure 16 is a hydrogen NMR spectrum of compound R-OBPDMAC.
  • Figure 17 is the carbon NMR spectrum of compound R-OBPDMAC.
  • Figure 18 is a mass spectrum of compound R-OBPDMAC.
  • the raw materials involved in the present invention are all conventional commercial products, and the specific operation methods and testing methods are conventional methods in the field; especially the specific preparation process of the electroluminescent device based on the chiral thermally activated delayed fluorescent material of the present invention and the materials of each layer are the current There are techniques, such as vacuum evaporation, vacuum degree ⁇ 2 ⁇ 10 -4 Pa, functional layer deposition rate of 2 ⁇ /s, host material deposition rate of 1 ⁇ /s, LiF layer deposition rate of 0.1 ⁇ /s, Al deposition Rate 8 ⁇ /s.
  • the inventiveness of the present invention is to provide a new chiral thermally activated delayed fluorescent material, and the doped host material is used together as a light-emitting layer of an organic electroluminescent device.
  • the present invention provides a chiral thermally activated delayed fluorescent material R/S-18,21-bis(10H-phenoxazine-10-yl)-3,4,5,6,7,8,9,10-octahydrodi Benzo[a,c]dinaphtho[2',1':5,6; 1'',2'':7,8] [1,4]Dioxin[2,3-i]phenazine (R/S-ODPPXZ) and R/S-16,17-bis(4-(10H-phenoxazin-10-yl)phenyl )-3,4,5,6,7,8,9,10-octahydrodinaphtho[2',1':5,6;1'',2'':7,8][1,4 ]dioxane[2,3-g]quinoxaline (R/S-ODQPXZ).
  • the structural formula is as follows: .
  • the specific reaction is as follows: add 0.45 g (3.12 g) to a 150 mL three-necked flask mmol) 4,5-difluorobenzene-1,2-diamine and 1.12 g (3.06 mmol) 3,6-dibromo-9,10-phenanthrenequinone, then add 100 mL of absolute ethanol as a solvent, under nitrogen Stir under protection, react at 80 °C for 2 hours, then filter the reaction solution, and recrystallize the filter cake with absolute ethanol to obtain 3,6-dibromo-11,12-difluorodibenzo[a,c]phene as a light yellow solid oxazine in 95% yield.
  • the eluent used in column chromatography is one of organic solvents with low polarity such as petroleum ether, isopentane, n-pentane, hexane, cyclohexane, etc., and another organic solvent with high polarity.
  • the volume ratio is 1:2 ⁇ 5.
  • Fig. 1 is the hydrogen nuclear magnetic spectrum of the compound R-ODPPXZ obtained above;
  • Fig. 2 is the carbon nuclear magnetic spectrum of the compound R-ODPPXZ obtained above;
  • Fig. 3 is the mass spectrum of the compound R-ODPPXZ obtained above;
  • Fig. 4 is the compound obtained above The HPLC spectrum of R-ODPPXZ;
  • Fig. 5 is the HPLC spectrum of the compound S-ODPPXZ obtained above.
  • the specific reaction is as follows: add 0.45 g (3.12 g) to a 150 mL three-necked flask mmol) 4,5-difluorobenzene-1,2-diamine and 1.12 g (3.04 mmol) 1,2-bis(4-bromophenyl)ethane-1,2-dione, followed by 100 mL of Water ethanol was used as a solvent, stirred under the protection of nitrogen, and reacted at 80 °C for 2 hours, then the reaction solution was filtered, and the filter cake was recrystallized with absolute ethanol to obtain a pale yellow solid 2,3-bis(4-bromophenyl)-6 , 7-Difluoroquinoxaline in 95% yield.
  • Chloromethane the volume ratio of 1:2 was separated and purified to obtain an orange solid 10,10'-(((6,7-difluoroquinoxaline-2,3-diyl)bis(4,1- phenylene)) bis(10H-phenoxazine) in 80% yield.
  • the eluent used in column chromatography is one of organic solvents with low polarity such as petroleum ether, isopentane, n-pentane, hexane, cyclohexane, etc., and another organic solvent with high polarity.
  • the volume ratio is 1:2 ⁇ 5.
  • Fig. 6 is the hydrogen nuclear magnetic spectrum of the compound R-ODQPXZ obtained above;
  • Fig. 7 is the carbon nuclear magnetic spectrum of the compound R-ODQPXZ obtained above;
  • Fig. 8 is the mass spectrum of the compound R-ODQPXZ obtained above;
  • Fig. 9 is the compound obtained above The HPLC spectrum of R-ODQPXZ;
  • Figure 10 is the HPLC spectrum of the compound S-ODQPXZ obtained above.
  • Pretreatment of glass anode select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; after cleaning the glass substrate with ethanol, UV-ozone processing to obtain a pretreated glass substrate.
  • ITO indium tin oxide
  • Vacuum evaporation carry out vacuum evaporation of each layer on the pretreated glass substrate by vacuum evaporation method, put the treated glass substrate into a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa
  • the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 7wt%R-ODPPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); the specific layer evaporation is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Performance evaluation of organic electroluminescent devices with the doping concentration of 7wt% R-ODPPXZ as the light-emitting layer Direct current was applied to the fabricated organic electroluminescent devices, using PhotoResearch A PR655 luminance meter was used to evaluate luminous performance; a computer-controlled Keithley Model 2400 SourceMeter was used to measure current-voltage characteristics. The luminescence properties of the organic electroluminescent device were measured under the condition of changing the applied DC voltage. Device performance is shown in Table 1, Table 2, and Figure 13.
  • Pretreatment of glass anode select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; after cleaning the glass substrate with ethanol, UV-ozone processing to obtain a pretreated glass substrate.
  • ITO indium tin oxide
  • Vacuum evaporation carry out vacuum evaporation of each layer on the pretreated glass substrate by vacuum evaporation method, put the treated glass substrate into a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa
  • the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 15wt%R-ODQPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); the specific layer evaporation is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Performance evaluation of organic electroluminescent devices with 15wt% doping concentration of R-ODQPXZ as the light-emitting layer Direct current was applied to the fabricated organic electroluminescent devices, using PhotoResearch A PR655 luminance meter was used to evaluate luminous performance; a computer-controlled Keithley Model 2400 SourceMeter was used to measure current-voltage characteristics. The luminescence properties of the organic electroluminescent device were measured under the condition of changing the applied DC voltage. Device performance is shown in Table 1, Table 2, and Figure 13.
  • FIG. 14 is the device efficiency diagram of the application example (1)
  • FIG. 15 is the device efficiency diagram of the application example (2).
  • Application example (3) the fabrication and performance evaluation of an organic electroluminescent device with a doping concentration of 3wt% R-ODPPXZ as the light-emitting layer, is the same as the above application example (1) R-ODPPXZ with a doping concentration of 7wt%
  • the fabrication and performance evaluation of organic electroluminescent devices with the light-emitting layer are consistent with the performance evaluation, in which CBP: 3wt% R-ODPPXZ (20 nm) is used as the light-emitting layer, and the rest remain unchanged.
  • the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/ /B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); the specific layer evaporation is a conventional technique; the organic electro- The luminescence properties of the light-emitting device were measured under the condition of changing the applied DC voltage; the maximum external quantum efficiency of the device was 12.9%.
  • the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 15wt%R-ODPPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); the specific layer evaporation is a conventional technique; the luminescence properties of the organic electroluminescence device are in the case of applying a DC voltage change The maximum external quantum efficiency of the device is 7.6%.
  • the circularly polarized organic electroluminescence device prepared by the R-ODPPXZ chiral orange-red photothermally activated delayed fluorescent material of the present invention has high external quantum efficiency, high luminous efficiency and low open circuit voltage, and is an excellent OLED material.
  • the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP:10wt%R-ODQPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); the specific layer evaporation is a conventional technique; the luminescence properties of the organic electroluminescence device are in the case of applying a DC voltage change The maximum external quantum efficiency of the device was 18.0%.
  • the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 20wt%R-ODQPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); the specific layer evaporation is a conventional technique; the luminescence properties of the organic electroluminescence device are in the case of applying a DC voltage change The maximum external quantum efficiency of the device is 20.7%.
  • the chiral thermally activated delayed fluorescent material and organic electroluminescent devices based on it have broad application prospects in the fields of 3D display, information storage and processing, circularly polarized light-emitting lasers, biological probes, and photocatalytic asymmetric synthesis.
  • the specific reaction is as follows: add 0.45 g (3.12 g) to a 150 mL three-necked flask mmol) 4,5-difluorobenzene-1,2-diamine and 1.12 g (3.06 mmol) 3,6-dibromo-9,10-phenanthrenequinone, then add 100 mL of absolute ethanol as a solvent, under nitrogen Stir under protection, react at 80 °C for 2 hours, then filter the reaction solution, and recrystallize the filter cake with absolute ethanol to obtain 3,6-dibromo-11,12-difluorodibenzo[a,c]phene as a light yellow solid oxazine in 95% yield.
  • the eluent used in column chromatography is one of organic solvents with low polarity such as petroleum ether, isopentane, n-pentane, hexane, cyclohexane, etc., and another organic solvent with high polarity.
  • the volume ratio is 1:2 ⁇ 5.
  • Fig. 16 is the H NMR spectrum of the compound R-OBPDMAC obtained above;
  • Fig. 17 is the C NMR spectrum of the compound R-OBPDMAC obtained above;
  • Fig. 18 is the mass spectrum of the compound R-OBPDMAC obtained above.
  • Pretreatment of glass anode Select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; wash the glass substrate with ethanol, and then treat it with UV-ozone to obtain Pretreated glass substrates.
  • ITO indium tin oxide
  • Vacuum evaporation carry out vacuum evaporation of each layer on the pretreated glass substrate by vacuum evaporation method, put the treated glass substrate into a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa
  • the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 7wt%R-OBPDMAC (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specific layer evaporation is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Performance evaluation of organic electroluminescent devices with 7wt% doping concentration of R-OBPDMAC as the light-emitting layer Direct current was applied to the fabricated organic electroluminescent devices, using PhotoResearch A PR655 luminance meter was used to evaluate luminous performance; a computer-controlled Keithley Model 2400 SourceMeter was used to measure current-voltage characteristics. The luminescence properties of the organic electroluminescence device were measured under the condition of changing the applied DC voltage; the maximum external quantum efficiency of the device was 13.0%.
  • Pretreatment of glass anode Select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; wash the glass substrate with ethanol, and then treat it with UV-ozone to obtain Pretreated glass substrates.
  • ITO indium tin oxide
  • Vacuum evaporation carry out vacuum evaporation of each layer on the pretreated glass substrate by vacuum evaporation method, put the treated glass substrate into a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa
  • the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 15wt%R-OBPDMAC (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specific layer evaporation is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Performance evaluation of organic electroluminescent devices with 15 wt% doping concentration of R-OBPDMAC as the light-emitting layer Direct current was applied to the fabricated organic electroluminescent devices, using PhotoResearch A PR655 luminance meter was used to evaluate luminous performance; a computer-controlled Keithley Model 2400 SourceMeter was used to measure current-voltage characteristics. The luminescence properties of the organic electroluminescence device were measured under the condition of changing the applied DC voltage; the maximum external quantum efficiency of the device was 10.5%.
  • Pretreatment of glass anode Select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; wash the glass substrate with ethanol, and then treat it with UV-ozone to obtain Pretreated glass substrates.
  • ITO indium tin oxide
  • Vacuum evaporation carry out vacuum evaporation of each layer on the pretreated glass substrate by vacuum evaporation method, put the treated glass substrate into a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa, the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specific layer evaporation is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Performance evaluation of organic electroluminescent devices with undoped light-emitting layers Direct current was applied to the fabricated organic electroluminescent devices, using PhotoResearch A PR655 luminance meter was used to evaluate luminous performance; a computer-controlled Keithley Model 2400 SourceMeter was used to measure current-voltage characteristics. The luminescence properties of the organic electroluminescence device were measured under the condition of changing the applied DC voltage; the maximum external quantum efficiency of the device was 2.7%.

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  • Electroluminescent Light Sources (AREA)

Abstract

一种基于手性热激活延迟荧光材料的电致发光器件，包括手性热激活延迟荧光材料掺杂的发光层，在阳极上依次真空蒸镀空穴注入层、空穴传输层、阻挡层、发光层、电子传输层、电子注入层、阴极，得到所述基于手性热激活延迟荧光材料的电致发光器件。所述的基于手性热激活延迟荧光材料的圆偏振电致发光器件可发射黄色或者橙红色荧光(λ＝548或600nm)，器件外量子效率EQE高达28.3％和20.3％，不对称因子为6.0×10 -4和2.4×10 -3，且具有驱动电压低，发光稳定性好等优点。

Description

基于手性热激活延迟荧光材料的电致发光器件及其制备方法 技术领域
本发明涉及有机电致发光材料领域，尤其涉及一种可工业化、性能好的基于手性热激活延迟荧光材料的电致发光器件及其制备方法。
 背景技术
电致发光(英文electroluminescent)，又可称电场发光，简称EL，是通过加在两电极的电压产生电场，被电场激发的电子碰击发光中心，而引致电子在能级间的跃迁、变化、复合导致发光的一种物理现象。一般认为是在强电场作用下，电子的能量相应增大，直至远远超过热平衡状态下的电子能量而成为过热电子，这过热电子在运动过程中可以通过碰撞使晶格离化形成电子、空穴对，当这些被离化的电子、空穴对复合或被激发的发光中心回到基态时便发出光来。从发光原理电致发光可以分为高场电致发光和低场电致发光。高场电致发光是一种体内发光效应。发光材料是一种半导体化合物，掺杂适当的杂质引进发光中心或形成某种介电状态。当它与电极或其他介质接触时，其势垒处于反向时，来自电极或界面态的电子，进人发光材料的高场区，被加速并成为过热电子。圆偏振发光（CPL）在3D成像、信息存储、量子计算等方面的潜在应用而受到广泛关注。同时，TADF有机发光材料无需贵金属即可理论上实现100 %的内量子效率而成为研究的热点。目前主要通过手性小分子片段直接嫁接到TADF分子骨架上而实现CPL-TADF，然而由于分子设计合成复杂而限制了其进一步的扩展，因此开发新型简单、高效的手性TADF材料成为当前的一个研究热点。
 技术问题
本发明公开了一种基于手性热激活延迟荧光材料的电致发光器件及其制备方法，手性热激活延迟荧光材料的化学名称为R/S-18,21-二（10H-吩恶嗪-10-基）-3,4,5,6,7,8,9,10-八氢二苯并[a，c]二萘并[2',1'：5,6; 1 '',2''：7,8] [1,4]二恶英[2,3-i]吩嗪或者R/S-16,17-双（4-（10H-吩恶嗪-10-基）苯基）-3,4,5,6,7,8,9,10-八氢二萘并[2'，1'：5,6; 1' '，2''：7,8] [1,4]二恶烷[2,3-g]喹喔啉，用以解决手性延迟荧光发光材料合成制备难、材料种类少、圆偏振延迟荧光器件效率低的难题；同时解决现有橙红光/红光TADF材料合成制备步骤多，原料昂贵，合成及纯化工艺复杂，产率不高，难于大规模量产的问题；尤其是，该手性热激活延迟荧光材料掺杂发光层制备的CP-OLED，实现其EQE超过20%，不对称因子g大于10 -3的目标。
技术解决方案
本发明采用如下技术方案：一种基于手性热激活延迟荧光材料的电致发光器件，包括手性热激活延迟荧光材料掺杂的发光层；本发明所述电致发光器件的发光层包括手性热激活延迟荧光材料，所述手性热激活延迟荧光材料作为客体材料掺杂主体材料作为发光层；进一步的，所述手性热激活延迟荧光材料的掺杂浓度为2～20wt%，指手性热激活延迟荧光材料占发光层总量的质量百分数。
本发明公开的基于手性热激活延迟荧光材料的电致发光器件由阳极、空穴注入层、空穴传输层、阻挡层、发光层、电子传输层、电子注入层、阴极组成；具体可以为，氧化铟锡（ITO）用作阳极、双吡嗪并[2,3-f：2'，3'-h]喹喔啉-2,3,6,7,10,11-己腈（HATCN）用作空穴注入层（HIL）、4,4'-（环己烷-1,1-二基）双（N，N-二-对甲苯基苯胺）（TAPC）用作空穴传输层（HTL）、三（4-（9H-咔唑-9-基）苯基）胺(TCTA)用作电子/激子阻挡层（EBL）、所述手性热激活延迟荧光材料作客体材料掺杂4,4'-二（9H-咔唑-9-基）-1,1'-联苯(CBP)主体材料共同用作发光层（EML）、4,6-双（3,5-二（吡啶-3-基）苯基）-2-甲基嘧啶(B3PYMPM)用作电子传输层（ETL）、8-羟基喹啉-锂（Liq）用作电子注入层（EIL）、铝（Al）用作阴极；有机电致发光器件规格为：ITO/HATCN（10nm）/TAPC（40 nm）/TCTA（10 nm）/CBP：R/S-TADF材料（Xwt%）（20nm）/B3PYMPM（50nm）/Liq（2nm）/Al（100 nm）。
本发明公开了一种电致发光器件用发光层，为手性热激活延迟荧光材料掺杂4,4'-二（9H-咔唑-9-基）-1,1'-联苯。
上述基于手性热激活延迟荧光材料的电致发光器件的制备方法为，在阳极上依次真空蒸镀空穴注入层、空穴传输层、阻挡层、发光层、电子传输层、电子注入层、阴极，得到所述基于手性热激活延迟荧光材料的电致发光器件。真空蒸镀为常规技术。
本发明所述手性热激活延迟荧光材料为化合物R-ODPPXZ、化合物S-ODPPXZ、化合物R-ODQPXZ或者化合物S-ODQPXZ，其化学结构式分别如下。
Figure 770230dest_path_image001
。
一方面：上述手性橙红光热激活延迟荧光材料的制备方法包括以下步骤：以10,10'-（11,12-二氟二苯并[a，c]吩嗪-3,6-二基）双（10H-吩恶嗪）、5,5',6,6',7,7',8,8'-八氢联萘酚为原料，反应制备得到所述手性橙红光热激活延迟荧光材料化合物R-ODPPXZ、化合物S-ODPPXZ。
Figure 421791dest_path_image003
  。
 进一步的，10,10'-（11,12-二氟二苯并[a，c]吩嗪-3,6-二基）双（10H-吩恶嗪）、5,5',6,6',7,7',8,8'-八氢联萘酚的摩尔比1∶0.8～1.1；反应在碱存在下、氮气保护下进行；反应的温度为40～100 °C，反应的时间为12～24 h。反应完毕后，萃取反应液，然后合并有机相，再抽滤，得到所述手性橙红光热激活延迟荧光材料；优选的，萃取溶剂可以是二氯甲烷、三氯甲烷、乙酸乙酯、冰醋酸中的任意一种或这些溶剂的某种组合。
另一方面：上述手性黄光热激活延迟荧光材料的制备方法包括以下步骤：以10,10'-（（（6,7-二氟喹喔啉-2,3-二基）双（4,1-亚苯基））双（10H-吩恶嗪）、5,5',6,6',7,7',8,8'-八氢联萘酚为原料，反应制备得到所述手性黄光热激活延迟荧光材料化合物R-ODQPXZ或者化合物S-ODQPXZ。
Figure 935949dest_path_image004
。
进一步的，10,10'-（（（6,7-二氟喹喔啉-2,3-二基）双（4,1-亚苯基））双（10H-吩恶嗪）、5,5',6,6',7,7',8,8'-八氢联萘酚的摩尔比1∶0.8～1.1；反应在碱存在下、氮气保护下进行；反应的温度为40～100 °C，反应的时间为12～24 h。反应完毕后，萃取反应液，然后合并有机相，再抽滤，得到所述手性黄光热激活延迟荧光材料；优选的，萃取溶剂可以是二氯甲烷、三氯甲烷、乙酸乙酯、冰醋酸中的任意一种或这些溶剂的某种组合。
本发明提供一种新型手性热激活延迟荧光材料的合成制备方法；以及基于所述手性热激活延迟荧光材料的OLED，实现其EQE超过20%，不对称因子大于10 -3的目标；用以解决手性延迟荧光发光材料合成制备难、材料种类少、圆偏振延迟荧光器件效率低的难题；同时解决现有橙红光/红光TADF材料合成制备步骤多，原料昂贵，合成及纯化工艺复杂，产率不高，难于大规模量产的问题。
对于本发明基于手性橙红光热激活延迟荧光材料所形成的有机电致发光器件的制备方法以及其他原料没有特殊的限制。利用本发明所形成的有机薄膜具有高表面光滑性、化学物理性质稳定高发光效率和圆偏振光性质，所形成的圆偏振有机电致发光器件性能良好。
 有益效果
本发明有益效果如下：1.本发明提供的R/S-18,21-二（10H-苯恶嗪-10-基）-3,4,5,6,7,8,9,10-八氢二苯并[a，c]二萘并[2',1'：5,6; 1 '',2''：7,8] [1,4]二恶英[2,3-i]吩嗪或者R/S-16,17-双（4-（10H-吩恶嗪-10-基）苯基）-3,4,5,6,7,8,9,10-八氢二萘并[2'，1'：5,6; 1' '，2''：7,8] [1,4]二恶烷[2,3-g]喹喔啉热激活延迟荧光材料具有刚性大平面扭曲结构和显著的内电荷转移（ICT）的特点，具有热激活延迟荧光性质（TADF）和圆偏振发光（CPL）性质，高荧光量子产率（PLQY）、热稳定性好等优点。
2. 基于本发明提供的手性热激活延迟荧光材料的CP-OLED器件，具有驱动电压低，发光稳定性好的优点，且制备的圆偏振器件的外量子效率EQE分别高达28.3%和20.3%，不对成因子g分别高达6×10 -4 和 2.4×10 -3。
3. 本发明提供的手性热激活延迟荧光材料合成制备步骤少，原料易得，合成及纯化工艺简单，产率高，可大规模合成制备。基于其的有机电致发光器件在照明、平板显示、传感、夜视及生物成像等领域具有很好的应用前景；圆偏振发光器件在3D成像、信息存储、量子计算等方面的也具有潜在的应用前景。
 附图说明
图1是实施例1制备所得的化合物R-ODPPXZ的核磁氢谱。
图2是实施例1制备所得的化合物R-ODPPXZ的核磁碳谱。
图3是实施例1制备所得的化合物R-ODPPXZ的质谱。
图4是实施例1制备所得的化合物R-ODPPXZ的HPLC谱。
图5是实施例1制备所得的化合物S-ODPPXZ的HPLC谱。
图6是实施例2制备所得的化合物R-ODQPXZ的核磁氢谱。
图7是实施例2制备所得的化合物R-ODQPXZ的核磁碳谱。
图8是实施例2制备所得的化合物R-ODQPXZ的质谱。
图9是实施例2制备所得的化合物R-ODQPXZ的HPLC谱。
图10是实施例2制备所得的化合物S-ODQPXZ的HPLC谱。
图11是实施例1和2制备所得化合物的圆二色光谱。
图12是实施例1和2制备所得化合物在薄膜条件下的圆偏振光谱。
图13是应用实施例一和二的器件性能图。
图14是应用实施例（一）的器件效率图。
图15是应用实施例（二）的器件效率图。
图16是化合物R-OBPDMAC的核磁氢谱。
图17是化合物R-OBPDMAC的核磁碳谱。
图18是化合物R-OBPDMAC的质谱。
 本发明的实施方式
本发明涉及的原料都为常规市售产品，具体操作方法以及测试方法为本领域常规方法；尤其基于本发明手性热激活延迟荧光材料的电致发光器件的具体制备过程以及各层材料为现有技术，比如真空蒸镀，真空度≤2×10 -4Pa，功能层沉积速率为2Å/s，主体材料的沉积速率为1Å/s，LiF层沉积速率为0.1Å/s，Al的沉积速率8Å/s。
本发明的创造性在于提供新的手性热激活延迟荧光材料，掺杂主体材料共同用作有机电致发光器件的发光层。
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的优点，而不是对本发明权利要求的限制。
本发明提供手性热激活延迟荧光材料R/S-18,21-二（10H-苯恶嗪-10-基）-3,4,5,6,7,8,9,10-八氢二苯并[a，c]二萘并[2',1'：5,6; 1 '',2''：7,8] [1,4]二恶英[2,3-i]吩嗪（R/S-ODPPXZ）和R/S-16,17-双（4-（10H-吩恶嗪-10-基）苯基）-3,4,5,6,7,8,9,10-八氢二萘并[2'，1'：5,6; 1' '，2''：7,8] [1,4]二恶烷[2,3-g]喹喔啉（R/S-ODQPXZ）。
结构式如下所示：。
实施例1。
Figure 65579dest_path_image005
。
反应具体如下：150 mL三口烧瓶中加入0.45 g(3.12 mmol) 4,5-二氟苯-1,2-二胺和1.12 g(3.06 mmol)3,6-二溴-9,10-菲醌，再加入100 mL无水乙醇作为溶剂，在氮气的保护下搅拌，80 ℃反应2小时，然后过滤反应液，滤饼用无水乙醇重结晶，得淡黄色固体3,6-二溴-11,12-二氟二苯并[a，c]吩嗪，产率为95%。
150 mL三口烧瓶中先后加入0.50 g（1.05 mmol）3,6-二溴-11,12-二氟二苯并[a，c]吩嗪、0.40 g（2.18 mmol）10H-吩恶嗪、0.41 g（4.27 mmol）叔丁醇钠、0.016 g（0.055 mmol）四氟硼酸三叔丁基膦、0.05 g（0.055 mmol）三（二亚苄基丙酮）二钯（0），再加入50 mL甲苯作溶剂，氮气保护下100 ℃加热反应；反应完毕后，用100 mL二氯甲烷萃取后，合并有机相并抽滤，产物采用柱层析（石油醚/二氯甲烷，体积比为1：2）的方法进行分离提纯，得到深红色固体10,10'-（11,12-二氟二苯并[a，c]吩嗪-3,6-二基）双（10H-吩恶嗪），产率为80%。
150 mL三口烧瓶中加入0.50 g(0.74 mmol) 10,10'-（11,12-二氟二苯并[a，c]吩嗪-3,6-二基）双（10H-吩恶嗪），0.22 g(0.75 mmol) R/S-5,5',6,6',7,7',8,8'-八氢联萘酚和0.35 g(2.53 mmol)碳酸钾，再加入DMF（50 mL）作为溶剂，在氮气的保护下70 ℃搅拌反应；反应完毕后，用100 mL二氯甲烷萃取后，合并有机相并抽滤；产物采用柱层析（石油醚/二氯甲烷，体积比为1：2）的方法进行分离提纯，得到最终产物R/S-18,21-二（10H-苯恶嗪-10-基）-3,4,5,6,7,8,9,10-八氢二苯并[a，c]二萘并[2',1'：5,6; 1 '',2''：7,8] [1,4]二恶英[2,3-i]吩嗪，产率为70%。
柱层析采用洗脱剂是由石油醚、异戊烷、正戊烷、己烷、环己烷等极性较小的有机溶剂中的一种与另一种极性较大的有机溶剂配比而成，如二氯甲烷、三氯甲烷、乙酸乙酯、乙醇等，其体积比为1：2～5。
R/S-5,5',6,6',7,7',8,8'-八氢联萘酚的选择可得到对应的手性产物。图1是上述所得的化合物R-ODPPXZ的核磁氢谱；图2是上述所得的化合物R-ODPPXZ的核磁碳谱；图3是上述所得的化合物R-ODPPXZ的质谱；图4是上述所得的化合物R-ODPPXZ的HPLC谱；图5是上述所得的化合物S-ODPPXZ的HPLC谱。化合物R-ODPPXZ结构检测具体如下： 1H NMR (400 MHz, CDCl 3) δ 9.65 (d, J = 8.5 Hz, 2H), 8.50 (d, J = 1.8 Hz, 2H), 8.15 (s, 2H), 7.77 (dd, J = 8.5, 1.8 Hz, 2H), 7.16 (s, 4H), 6.75 (dd, J = 7.9, 1.5 Hz, 4H), 6.68 (td, J = 7.6, 1.4 Hz, 4H), 6.59 (td, J = 7.7, 1.6 Hz, 4H), 6.05 (dd, J = 7.9, 1.4 Hz, 4H), 2.92 – 2.75 (m, 6H), 2.53 (dt, J = 17.6, 6.0 Hz, 2H), 1.92 – 1.84 (m, 6H), 1.78 – 1.71 (m, 2H)； 13C NMR (101 MHz, CDCl 3) δ 153.29, 150.97, 143.98, 141.12, 140.99, 140.61, 137.00, 135.53, 134.13, 133.73, 130.94, 130.35, 130.02, 129.46, 125.73, 123.33, 121.69, 119.72, 118.61, 115.65, 113.32, 29.39, 27.76, 22.80, 22.66；MALDI-TOF MS (ESI, m/z) calcd for C 64H 44N 4O 4 [M +]: 932.34, Found: 932.701。
实施例2。
Figure 739006dest_path_image006
。
反应具体如下：150 mL三口烧瓶中加入0.45 g(3.12 mmol) 4,5-二氟苯-1,2-二胺和1.12 g(3.04 mmol) 1,2-双（4-溴苯基）乙烷-1,2-二酮，再加入100 mL无水乙醇作为溶剂，在氮气的保护下搅拌，80 ℃反应2小时，然后过滤反应液，滤饼用无水乙醇重结晶，得淡黄色固体2,3-双（4-溴苯基）-6,7-二氟喹喔啉，产率为95%。
150 mL三口烧瓶中先后加入1.00 g（2.10 mmol）2,3-双（4-溴苯基）-6,7-二氟喹喔啉、0.80 g（4.36 mmol）10H-吩恶嗪、1.00 g（10.4 mmol）叔丁醇钠、0.032 g（0.11 mmol）四氟硼酸三叔丁基膦、0.10 g（0.11 mmol）三（二亚苄基丙酮）二钯（0），再加入50 mL甲苯作溶剂，氮气保护下100 ℃加热反应；反应完毕后，用100 mL二氯甲烷萃取后，合并有机相并抽滤，产物采用柱层析（石油醚/二氯甲烷，体积比为1：2）的方法进行分离提纯，得到橙色固体10,10'-（（（6,7-二氟喹喔啉-2,3-二基）双（4,1-亚苯基））双（10H-吩恶嗪），产率为80%。
150 mL三口烧瓶中加入0.50 g(0.73 mmol) 10,10'-（（（6,7-二氟喹喔啉-2,3-二基）双（4,1-亚苯基））双（10H-吩恶嗪），0.21 g(0.71 mmol) R/S-5,5',6,6',7,7',8,8'-八氢联萘酚和0.25 g(1.81 mmol)碳酸钾，再加入DMF（50 mL）作为溶剂，在氮气的保护下70 ℃搅拌反应；反应完毕后，用100 mL二氯甲烷萃取后，合并有机相并抽滤；产物采用柱层析（石油醚/二氯甲烷，体积比为1：2）的方法进行分离提纯，得到最终产物R/S-16,17-双（4-（10H-吩恶嗪-10-基）苯基）-3,4,5,6,7,8,9,10-八氢二萘并[2'，1'：5,6; 1' '，2''：7,8] [1,4]二恶烷[2,3-g]喹喔啉，产率为70%。
柱层析采用洗脱剂是由石油醚、异戊烷、正戊烷、己烷、环己烷等极性较小的有机溶剂中的一种与另一种极性较大的有机溶剂配比而成，如二氯甲烷、三氯甲烷、乙酸乙酯、乙醇等，其体积比为1：2～5。
R/S-5,5',6,6',7,7',8,8'-八氢联萘酚的选择可得到对应的手性产物。图6是上述所得的化合物R-ODQPXZ的核磁氢谱；图7是上述所得的化合物R-ODQPXZ的核磁碳谱；图8是上述所得的化合物R-ODQPXZ的质谱；图9是上述所得的化合物R-ODQPXZ的HPLC谱；图10是上述所得的化合物S-ODQPXZ的HPLC谱。化合物R-ODQPXZ结构检测具体如下： 1H NMR (400 MHz, CDCl 3) δ 8.04 (s, 2H), 7.77 (d, J = 8.3 Hz, 4H), 7.40 (d, J = 8.3 Hz, 4H), 7.15 (d, J = 8.3 Hz, 2H), 7.09 (d, J = 8.2 Hz, 2H), 6.71 (dd, J = 7.8, 1.3 Hz, 4H), 6.64 (t, J = 7.0 Hz, 2H), 6.57-6.49 (m, 4H), 5.97 (d, J = 7.9 Hz, 4H), 2.92-2.74 (m, 7H), 2.51 (dt, J = 16.9, 5.7 Hz, 2H), 1.92-1.82 (m, 7H), 1.73 (dt, J = 13.3, 5.5 Hz, 2H).   13C NMR (101 MHz, CDCl 3) δ 153.06, 151.86, 150.86, 143.90, 139.30, 139.06, 136.96, 135.52, 133.94, 132.59, 130.86, 130.07, 130.04, 123.41, 121.56, 120.00, 118.50, 115.55, 113.15, 29.37, 27.74, 22.78, 22.64. MALDI-TOF MS (ESI, m/z) calcd for C 64H 46N 4O 4 [M +]: 934.35, Found: 935.660。
由上述检测结果可知，化合物R-ODPPXZ和R-ODQPXZ的结构正确。
以下通过应用实施例说明本发明合成的化合物在器件中作为发光层客体材料的应用效果。
应用实施例。
（一）掺杂浓度为7wt%的R-ODPPXZ为发光层的有机电致发光器件的制作与性能评价：掺杂浓度为7wt%的R-ODPPXZ为发光层的有机电致发光器件的制作步骤如下。
（1）玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将所述玻璃基板洗净后，再用UV-臭氧进行处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP∶7wt%R-ODPPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm)；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
掺杂浓度为7wt%的R-ODPPXZ为发光层的有机电致发光器件的性能评价：对所制作的有机电致发光器件施加直流电流，使用PhotoResearch PR655亮度计来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的。器件性能见表1、表2和图13。
(二)掺杂浓度为15wt%的R-ODQPXZ为发光层的有机电致发光器件的制作与性能评价：掺杂浓度为15wt%的R-ODQPXZ为发光层的有机电致发光器件的制作步骤如下。
（1）玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将所述玻璃基板洗净后，再用UV-臭氧进行处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP∶15wt%R-ODQPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm)；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
掺杂浓度为15wt%的R-ODQPXZ为发光层的有机电致发光器件的性能评价：对所制作的有机电致发光器件施加直流电流，使用PhotoResearch PR655亮度计来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的。器件性能见表1、表2和图13。
Figure 295889dest_path_image007
。
图14是应用实施例（一）的器件效率图；图15是应用实施例（二）的器件效率图。
应用实施例（三），掺杂浓度为3wt%的R-ODPPXZ为发光层的有机电致发光器件的制作与性能评价，与上述应用实施例（一）掺杂浓度为7wt%的R-ODPPXZ为发光层的有机电致发光器件的制作与性能评价一致，其中CBP∶3wt%R-ODPPXZ (20 nm)作为发光层，其余不变，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/ /B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm)；具体各层蒸镀为常规技术；所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的；器件的最大外量子效率为12.9%。
应用实施例（四），掺杂浓度为15wt%的R-ODPPXZ为发光层的有机电致发光器件的制作与性能评价，与上述应用实施例（一）掺杂浓度为7wt%的R-ODPPXZ为发光层的有机电致发光器件的制作与性能评价一致，其中CBP∶15wt%R-ODPPXZ (20 nm) 作为发光层，其余不变，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP∶15wt%R-ODPPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm)；具体各层蒸镀为常规技术；所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的；器件的最大外量子效率为7.6%。
可看出，本发明R-ODPPXZ手性橙红光热激活延迟荧光材料制备的圆偏振有机电致发光器件外量子效率高，具有高的发光效率、开路电压低，是一种优异的OLED材料。
应用实施例（五），掺杂浓度为10wt%的R-ODQPXZ为发光层的有机电致发光器件的制作与性能评价，与上述应用实施例（一）掺杂浓度为7wt%的R-ODPPXZ为发光层的有机电致发光器件的制作与性能评价一致，其中CBP∶10wt%R-ODQPXZ (20 nm) 作为发光层，其余不变，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP∶10wt%R-ODQPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm)；具体各层蒸镀为常规技术；所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的；器件的最大外量子效率为18.0%。
应用实施例（六）掺杂浓度为20wt%的R-ODQPXZ为发光层的有机电致发光器件的制作与性能评价，与上述应用实施例（一）掺杂浓度为7wt%的R-ODPPXZ为发光层的有机电致发光器件的制作与性能评价一致，其中CBP∶20wt%R-ODQPXZ (20 nm) 作为发光层，其余不变，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP∶20wt%R-ODQPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm)；具体各层蒸镀为常规技术；所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的；器件的最大外量子效率为20.7%。
本发明提供的基于该材料有机电致发光器件可发射黄色或者橙红色荧光（λ=548或600 nm），器件外量子效率EQE高达28.3%和20.3%，不对称因子为6.0×10 -4和2.4×10 -3，且具有驱动电压低，发光稳定性好等优点。该手性热激活延迟荧光材料和基于其的有机电致发光器件在3D显示，信息存储与处理，圆偏振发光激光器，生物探针，光催化不对称合成等领域具有广泛的应用前景。
以R/S-18,21-双（9,9-二甲基吖啶-10-基）-3,4,5,6,7,8,9,10-八氢二苯并[a，c]二萘并[2'，1'： 5,6; 1''，2''：7,8] [1,4]二恶英[2,3-i]吩嗪（R/S-OBPDMAC）作对比：
Figure 297343dest_path_image008
。
Figure 230664dest_path_image009
。
反应具体如下：150 mL三口烧瓶中加入0.45 g(3.12 mmol) 4,5-二氟苯-1,2-二胺和1.12 g(3.06 mmol)3,6-二溴-9,10-菲醌，再加入100 mL无水乙醇作为溶剂，在氮气的保护下搅拌，80 ℃反应2小时，然后过滤反应液，滤饼用无水乙醇重结晶，得淡黄色固体3,6-二溴-11,12-二氟二苯并[a，c]吩嗪，产率为95%。
150 mL三口烧瓶中先后加入0.50 g（1.05 mmol）3,6-二溴-11,12-二氟二苯并[a，c]吩嗪、0.50 g（2.38 mmol）9,9-二甲基吖啶、0.41 g（4.27 mmol）叔丁醇钠、0.016 g（0.055 mmol）四氟硼酸三叔丁基膦、0.05 g（0.055 mmol）三（二亚苄基丙酮）二钯（0），再加入50 mL甲苯作溶剂，氮气保护下100 ℃加热反应；反应完毕后，用100 mL二氯甲烷萃取后，合并有机相并抽滤，产物采用柱层析（石油醚/二氯甲烷，体积比为1：2）进行分离提纯，得到橙色固体3,6-双（9,9-二甲基吖啶-10-基）-11,12-二氟二苯并[a,c]吩嗪，产率80%。
150 mL三口烧瓶中加入0.50 g(0.68 mmol) 3,6-双（9,9-二甲基吖啶-10-基）-11,12-二氟二苯并[a，c]吩嗪，0.22 g(0.75 mmol) R/S-5,5',6,6',7,7',8,8'-八氢联萘酚和0.35 g(2.53 mmol)碳酸钾，再加入DMF（50 mL）为溶剂，在氮气下70 ℃搅拌反应；反应完毕后，用100 mL二氯甲烷萃取后，合并有机相并抽滤；产物采用柱层析（石油醚/二氯甲烷，体积比为1：2）的方法进行分离提纯，得到最终产物R/S-18,21-双（9,9-二甲基吖啶-10-基）-3,4,5,6,7,8,9,10-八氢二苯并[a,c]二萘并[2',1':5,6; 1'',2'':7,8] [1,4]二恶英[2,3-i]吩嗪，产率70%。
柱层析采用洗脱剂是由石油醚、异戊烷、正戊烷、己烷、环己烷等极性较小的有机溶剂中的一种与另一种极性较大的有机溶剂配比而成，如二氯甲烷、三氯甲烷、乙酸乙酯、乙醇等，其体积比为1：2～5。
R/S-5,5',6,6',7,7',8,8'-八氢联萘酚的选择可得到对应的手性产物。图16是上述所得的化合物R-OBPDMAC的核磁氢谱；图17是上述所得的化合物R-OBPDMAC的核磁碳谱；图18是上述所得的化合物R-OBPDMAC的质谱。化合物R-OBPDMAC结构检测具体如下： 1H NMR (400 MHz, CDCl 3) δ 9.67 (d, J = 8.5 Hz, 2H), 8.41 (d, J = 1.8 Hz, 2H), 8.15 (s, 2H), 7.73 (dd, J = 8.5, 1.8 Hz, 2H), 7.52-7.40 (m, 4H), 7.18-7.10 (m, 4H), 6.99-6.83 (m, 8H), 6.39-6.24 (m, 4H), 2.94-2.72 (m, 6H), 2.51 (dt, J = 17.6, 5.8 Hz, 2H), 1.84 (dd, J = 12.8, 6.2 Hz, 6H), 1.77 (t, J = 10.4 Hz, 2H), 1.71 (s, 12H)； 13C NMR (101 MHz, CDCl 3) δ 153.19, 151.02, 143.30, 141.35, 140.68, 140.58, 136.98, 135.49, 133.92, 131.61, 130.19, 130.11, 130.02, 129.18, 126.47, 126.04, 125.52, 120.76, 119.74, 118.65, 114.05, 36.01, 31.70, 29.39, 27.75, 22.80, 22.67；MALDI-TOF MS (ESI, m/z) calcd for C 70H 56N 4O 2 [M +]: 984.44, Found: 984.827。
对比应用例。
（一）掺杂浓度为7wt%的R-OBPDMAC为发光层的有机电致发光器件的制作与性能评价：掺杂浓度为7wt%的R-OBPDMAC为发光层的有机电致发光器件的制作步骤如下。
（1）玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将玻璃基板洗净后，再用UV-臭氧处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP∶7wt%R-OBPDMAC (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm) ；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
掺杂浓度为7wt%的R-OBPDMAC为发光层的有机电致发光器件的性能评价：对所制作的有机电致发光器件施加直流电流，使用PhotoResearch PR655亮度计来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的；器件的最大外量子效率为13.0%。
（二）掺杂浓度为15wt%的R-OBPDMAC为发光层的有机电致发光器件的制作与性能：掺杂浓度为15wt%的R-OBPDMAC为发光层的有机电致发光器件的制作步骤如下。
（1）玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将玻璃基板洗净后，再用UV-臭氧处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP∶15wt%R-OBPDMAC (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm) ；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
掺杂浓度为15wt%的R-OBPDMAC为发光层的有机电致发光器件的性能评价：对所制作的有机电致发光器件施加直流电流，使用PhotoResearch PR655亮度计来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的；器件的最大外量子效率为10.5%。
 (三) 未掺杂发光层的有机电致发光器件的制作与性能评价：未掺杂发光层的有机电致发光器件的制作步骤如下。
（1）玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将玻璃基板洗净后，再用UV-臭氧处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm) ；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
未掺杂发光层的有机电致发光器件的性能评价：对所制作的有机电致发光器件施加直流电流，使用PhotoResearch PR655亮度计来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的；器件的最大外量子效率为2.7%。

Claims (10)

  1. 一种基于手性热激活延迟荧光材料的电致发光器件，包括手性热激活延迟荧光材料掺杂的发光层，其特征在于：所述手性热激活延迟荧光材料为化合物R-ODPPXZ、化合物S-ODPPXZ、化合物R-ODQPXZ或者化合物S-ODQPXZ。
  2. 根据权利要求1所述基于手性热激活延迟荧光材料的电致发光器件，其特征在于，所述基于手性热激活延迟荧光材料的电致发光器件由阳极、空穴注入层、空穴传输层、阻挡层、发光层、电子传输层、电子注入层、阴极组成。
  3. 根据权利要求1所述基于手性热激活延迟荧光材料的电致发光器件，其特征在于，所述手性热激活延迟荧光材料的掺杂浓度为2～20wt%。
  4. 根据权利要求1所述基于手性热激活延迟荧光材料的电致发光器件，其特征在于，所述发光层由所述手性热激活延迟荧光材料掺杂4,4'-二（9H-咔唑-9-基）-1,1'-联苯得到。
  5. 根据权利要求1所述基于手性热激活延迟荧光材料的电致发光器件，其特征在于，以10,10'-（11,12-二氟二苯并[a，c]吩嗪-3,6-二基）双（10H-吩恶嗪）、5,5',6,6',7,7',8,8'-八氢联萘酚为原料，反应制备得到所述手性热激活延迟荧光材料R1和S1；或者以10,10'-（（（6,7-二氟喹喔啉-2,3-二基）双（4,1-亚苯基））双（10H-吩恶嗪）、5,5',6,6',7,7',8,8'-八氢联萘酚为原料，反应制备得到所述手性热激活延迟荧光材料R2和S2。
  6. 根据权利要求5所述基于手性热激活延迟荧光材料的电致发光器件，其特征在于，10,10'-（11,12-二氟二苯并[a，c]吩嗪-3,6-二基）双（10H-吩恶嗪）、5,5',6,6',7,7',8,8'-八氢联萘酚的摩尔比1∶0.8～1.1；10,10'-（（（6,7-二氟喹喔啉-2,3-二基）双（4,1-亚苯基））双（10H-吩恶嗪）、5,5',6,6',7,7',8,8'-八氢联萘酚的摩尔比1∶0.8～1.1；所述反应在碱存在下、氮气保护下进行，反应的温度为40～100 ℃，反应的时间为12～24 h。
  7. 权利要求1所述基于手性热激活延迟荧光材料的电致发光器件的制备方法，其特征在于，在阳极上依次真空蒸镀空穴注入层、空穴传输层、阻挡层、发光层、电子传输层、电子注入层、阴极，得到所述基于手性热激活延迟荧光材料的电致发光器件。
  8. 电致发光器件用发光层，其特征在于，为手性热激活延迟荧光材料掺杂4,4'-二（9H-咔唑-9-基）-1,1'-联苯。
  9. 权利要求8所述电致发光器件用发光层在制备权利要求1所述基于手性热激活延迟荧光材料的电致发光器件中的应用。
  10. 权利要求1所述基于手性热激活延迟荧光材料的电致发光器件在制备电致发光设备中的应用。
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