WO2022183900A1 - Dispositif électroluminescent organique comprenant un matériau à fluorescence retardée activée thermiquement utilisé en tant que matériau de couche électroluminescente - Google Patents

Dispositif électroluminescent organique comprenant un matériau à fluorescence retardée activée thermiquement utilisé en tant que matériau de couche électroluminescente Download PDF

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WO2022183900A1
WO2022183900A1 PCT/CN2022/076179 CN2022076179W WO2022183900A1 WO 2022183900 A1 WO2022183900 A1 WO 2022183900A1 CN 2022076179 W CN2022076179 W CN 2022076179W WO 2022183900 A1 WO2022183900 A1 WO 2022183900A1
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fluorescent material
thermally activated
activated delayed
independently selected
emitting device
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PCT/CN2022/076179
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English (en)
Chinese (zh)
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孟鸿
吴李杰
薛网娟
张鑫康
孟智敏
贺耀武
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北京大学深圳研究生院
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Priority claimed from CN202110224872.6A external-priority patent/CN113072570B/zh
Priority claimed from CN202110224292.7A external-priority patent/CN113072569A/zh
Priority claimed from CN202110238720.1A external-priority patent/CN113072571B/zh
Application filed by 北京大学深圳研究生院 filed Critical 北京大学深圳研究生院
Publication of WO2022183900A1 publication Critical patent/WO2022183900A1/fr

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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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/66—Arsenic compounds
    • C07F9/70—Organo-arsenic compounds
    • C07F9/80—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/94—Bismuth compounds
    • 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

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  • the invention relates to the technical field of organic optoelectronic materials, in particular to an organic light-emitting device using a thermally activated delayed fluorescent material as a material for a light-emitting layer.
  • OLED Organic Light Emitting Diodes
  • OLED is a type of device that uses organic materials to generate light under the action of an electric field and is excited by current or voltage, mostly using a sandwich structure.
  • OLED has attracted much attention in the field of new display and lighting technology due to its incomparable advantages such as saturated color quality, low power consumption, fast response speed, and large area preparation.
  • OLED is mainly used in the display screen field of computers and mobile phones, as well as in the field of home, shopping mall and vehicle lighting, and will expand to the application field of large-size display products in the future.
  • Light-emitting material is the core material of OLED.
  • three generations of light-emitting materials have been developed, namely fluorescent material, phosphorescent material and thermally activated delayed fluorescent material (Thermally Activated Delayed Fluorescence, TADF).
  • fluorescent materials have low efficiency
  • phosphorescent materials need to use noble metals
  • blue phosphorescent materials have poor stability
  • TADF materials can achieve 100% internal quantum efficiency and low cost, so they are currently the most commercially promising research hotspots.
  • the currently commonly used TADF material has a large fluorescence emission spectrum Full Width at Half Maximum (FWHM) value, resulting in low color purity and poor monochromaticity of the device.
  • MR-TADF multiple resonance-induced thermally activated delayed fluorescence
  • HOMO/LUMO separation can be achieved while minimizing long-range charge transfer states, enabling high-efficiency and narrow-band luminescence.
  • the luminescent color of MR-TADF materials is difficult to control and is accompanied by a severe roll-off of device efficiency, which largely limits the further application of MR-TADF materials in the field of full-color display and lighting.
  • the purpose of the present invention is to provide an organic light-emitting device using a thermally activated delayed fluorescent material as a material for the light-emitting layer, aiming to solve the problems of low color purity and low luminous efficiency of the light-emitting material of the existing organic light-emitting device. question.
  • thermoly activated delayed fluorescent material includes a thermally activated delayed red fluorescent material, a thermally activated delayed blue fluorescent material or a seven-membered ring thermally activated delayed fluorescent material.
  • the general formula of the thermally activated delayed red fluorescent material is:
  • X 1 , X 2 , X 3 and X 4 are each independently selected from NR, O, S, AsR or BiR, and R in said NR, AsR and BiR are each independently selected from hydrogen, deuterium, alkyl, mono Ring aromatic hydrocarbon, fused ring aromatic hydrocarbon, monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon; Ring A, Ring C, Ring D, Ring E are independently selected from five-membered ring, six-membered ring or seven-membered ring; R A , R C , R D , R E are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl or aromatic groups;
  • the general formula of the thermally activated delayed blue light fluorescent material is:
  • M 101 is B
  • Ar101 is benzene ring, thiophene or selenophene
  • X 101 is N, Bi or As
  • Ar102 and Ar103 independently select thiophene, furan, benzene, benzothiophene or benzofuran
  • R 101 -R 102 independently select benzene and substituted aryl and heteroaryl;
  • Ar 201 -Ar 204 are independently selected from benzene, thiophene, furan, pyridine or substituted above-mentioned aryl or heteroaryl
  • R 201 -R 212 are independently selected from hydrogen, deuterium, cyano or alkyl chain
  • X 101 is selected from hydrogen, deuterium, halogen, cyano, alkyl chain or benzene, thiophene, furan, carbazole, pyridine, quinoline, isoquinoline and substituted aryl or heteroaryl groups above.
  • the present invention uses the compound of the above general formula as the light-emitting material of the organic light-emitting device, which can provide full-color display for the organic light-emitting device, and has the advantages of high luminous efficiency, high color purity and small efficiency roll-off, etc., which can effectively improve the Device Stability and Operating Life.
  • FIG. 1 is a schematic structural diagram of an organic light-emitting device prepared by the present invention.
  • FIG. 2 is a schematic structural diagram of another organic light-emitting device prepared by the present invention.
  • Example 3 is a graph showing the results of a thermal stability test of a seven-membered ring thermally activated delayed fluorescent material in Example 28 of the present invention.
  • Example 4 is a graph showing the test results of the emission spectrum of the seven-membered ring thermally activated delayed fluorescent material in Example 28 of the present invention.
  • the present invention provides an organic light-emitting device and a display device.
  • a display device In order to make the objectives, technical solutions and effects of the present invention clearer and clearer, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
  • the organic light-emitting device of the present invention and the thermally activated delayed fluorescent material used in the light-emitting layer in the organic light-emitting device are further introduced below through specific examples, wherein the thermally activated delayed fluorescent material includes a thermally activated delayed red fluorescent material , thermally activated delayed blue light fluorescent material and seven-membered ring thermally activated delayed fluorescent material.
  • the light-emitting layer in the present invention includes a host material and a guest material, and the host material may be mCP, mCBP, CBP, etc., but is not limited thereto; the guest material is the thermally activated delayed red fluorescent material, The thermally activated delayed blue light fluorescent material or the seven-membered ring thermally activated delayed fluorescent material.
  • the device structure of the organic light-emitting device of the present invention is preferably: substrate/anode/hole transport layer/light-emitting layer/electron transport layer/cathode, substrate/anode/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/ Cathode, Substrate/Anode/Hole Injection Layer/Hole Transport Layer/Light Emitting Layer/Electron Transport Layer/Electron Injection Layer/Cathode, Substrate/Anode/Hole Injection Layer/Hole Transport Layer/Exciton Blocking Layer/Light Emitting Layer /electron transport layer/electron injection layer/cathode, etc.
  • the structure of the organic light emitting device is not limited to this.
  • the compounds not mentioned in the examples are all raw materials obtained through commercial channels.
  • the solvents and reagents used in the examples can be purchased from the domestic chemical market. In addition, those skilled in the art can also synthesize them by known methods.
  • the material used in the light-emitting layer of the organic light-emitting device is a thermally activated delayed red fluorescent material, and the general formula of the thermally activated delayed red fluorescent material is:
  • X 1 , X 2 , X 3 and X 4 are each independently selected from NR, O, S, AsR or BiR, and R in said NR, AsR and BiR are each independently selected from hydrogen, deuterium, alkyl, mono Ring aromatic hydrocarbon, fused ring aromatic hydrocarbon, monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon; Ring A, Ring C, Ring D, Ring E are independently selected from five-membered ring, six-membered ring or seven-membered ring; R A , R C , R D , R E are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl or aromatic groups.
  • the structure of the thermally activated delayed red fluorescent material is selected from one of the following formulas:
  • X 1 , X 2 , X 3 , X 4 are each independently selected from N, As or Bi, and R 1 to R 28 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkane group, alkenyl, alkoxy or thioalkoxy, monocyclic aromatic hydrocarbon or fused ring aromatic hydrocarbon, monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon.
  • the structure of the thermally activated delayed red fluorescent material is shown in the following formula:
  • the structure of the thermally activated delayed red fluorescent material is selected from one of the following formulas:
  • X is independently selected from O or S;
  • R 1 -R 20 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, alkenyl, alkoxy or thioalkane Oxygen, monocyclic aromatic hydrocarbons or fused ring aromatic hydrocarbons, monocyclic heteroaromatic hydrocarbons or fused ring heteroaromatic hydrocarbons.
  • the structure of the thermally activated delayed red fluorescent material is shown in the following formula:
  • X is independently selected from O or S;
  • R 1 -R 36 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, alkenyl, alkoxy or thioalkane Oxygen, monocyclic aromatic hydrocarbons or fused ring aromatic hydrocarbons, monocyclic heteroaromatic hydrocarbons or fused ring heteroaromatic hydrocarbons.
  • the structure of the thermally activated delayed red fluorescent material is shown in the following formula:
  • X is independently selected from O, S or Se.
  • the structure of the thermally activated delayed red fluorescent material is shown in the following formula:
  • R 1 -R 44 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, alkenyl, alkoxy or thioalkoxy, monocyclic aromatic hydrocarbons or fused ring aromatic hydrocarbons , monocyclic heteroaromatic hydrocarbons or fused ring heteroaromatic hydrocarbons.
  • the structure of the thermally activated delayed red fluorescent material is selected from one of the following formulas:
  • the present invention also provides a method for preparing a thermally activated delayed red fluorescent material with the above general formula:
  • Y 1 -Y 4 are independently selected from F, Cl, Br, I; Y 5 and Y 6 are independently selected from H, F, Cl, Br, I; X is selected from N, As, Bi A sort of.
  • the main flow of the preparation method in the present invention firstly, the intermediate is prepared by CX coupling reaction; then, n-butyllithium or tert-butyllithium is added to carry out ortho-metalation; then, boron tribromide is added to carry out lithium-boron Or lithium-phosphorus metal exchange, adding a Bronsted base such as N,N-diisopropylethylamine, and performing a tandem Bora Fried-Crafts reaction to obtain the target product.
  • a Bronsted base such as N,N-diisopropylethylamine
  • Examples 1-9 briefly describe the preparation method of the thermally activated delayed red fluorescent material used in the light-emitting layer of the organic light-emitting device of the present invention.
  • n-butyllithium in n-hexane solution (3.0eq) was slowly added to the tert-butylbenzene solution of precursor 1-E (1.0eq) at 0°C, stirred for 0.5 hours, and then heated to 60°C, the reaction 2 hours. After the reaction was completed, the temperature was lowered to -40° C., boron tribromide (3.6eq) was slowly added, and stirring was continued at room temperature for 0.5 hours. N,N-diisopropylethylamine (5.0 eq) was added at 0°C and the reaction was continued at 120°C for 5 hours and then stopped.
  • n-butyllithium in n-hexane solution (3.0eq) was slowly added to the tert-butylbenzene solution of precursor 2-E (1.0eq) at 0°C, stirred for 0.5 hours, and then heated to 60°C for the reaction. 2 hours. After the reaction was completed, the temperature was lowered to -40° C., boron tribromide (3.6eq) was slowly added, and stirring was continued at room temperature for 0.5 hours. N,N-diisopropylethylamine (5.0 eq) was added at 0°C and the reaction was continued at 120°C for 5 hours and then stopped.
  • n-butyllithium in n-hexane solution (3.0eq) was slowly added to the tert-butylbenzene solution of precursor 3-C (1.0eq) at 0°C, stirred for 0.5 hours, and then heated to 60°C, the reaction 2 hours. After the reaction was completed, the temperature was lowered to -40° C., boron tribromide (3.6eq) was slowly added, and stirring was continued at room temperature for 0.5 hours. N,N-diisopropylethylamine (5.0 eq) was added at 0°C and the reaction was continued at 120°C for 5 hours and then stopped.
  • n-butyllithium in n-hexane solution (3.0eq) was slowly added to the tert-butylbenzene solution of precursor 4-E (1.0eq) at 0°C, stirred for 0.5 hours, and then heated to 60°C, the reaction 2 hours. After the reaction was completed, the temperature was lowered to -40° C., boron tribromide (3.6eq) was slowly added, and stirring was continued at room temperature for 0.5 hours. N,N-diisopropylethylamine (5.0 eq) was added at 0°C and the reaction was continued at 120°C for 5 hours and then stopped.
  • n-butyllithium in n-hexane solution (3.0eq) was slowly added to the tert-butylbenzene solution of precursor 5-E (1.0eq) at 0°C, stirred for 0.5 hours, and then heated to 60°C, the reaction 2 hours. After the reaction was completed, the temperature was lowered to -40° C., boron tribromide (3.6eq) was slowly added, and stirring was continued at room temperature for 0.5 hours. N,N-diisopropylethylamine (5.0 eq) was added at 0°C and the reaction was continued at 120°C for 5 hours and then stopped.
  • n-butyllithium in n-hexane solution (3.0eq) was slowly added to the tert-butylbenzene solution of precursor 6-C (1.0eq) at 0°C, stirred for 0.5 hours, and then heated to 60°C, the reaction 2 hours. After the reaction was completed, the temperature was lowered to -40° C., boron tribromide (3.6eq) was slowly added, and stirring was continued at room temperature for 0.5 hours. N,N-diisopropylethylamine (5.0 eq) was added at 0°C and the reaction was continued at 120°C for 5 hours and then stopped.
  • n-butyllithium in n-hexane solution (3.0eq) was slowly added to the tert-butylbenzene solution of precursor 7-C (1.0eq) at 0°C, stirred for 0.5 hours, and then heated to 60°C, the reaction 2 hours. After the reaction was completed, the temperature was lowered to -40° C., boron tribromide (3.6eq) was slowly added, and stirring was continued at room temperature for 0.5 hours. N,N-diisopropylethylamine (5.0 eq) was added at 0°C and the reaction was continued at 120°C for 5 hours and then stopped.
  • n-butyllithium in n-hexane solution (3.0eq) was slowly added to the tert-butylbenzene solution of precursor 8-E (1.0eq) at 0°C, stirred for 0.5 hours, and then heated to 60°C, the reaction 2 hours. After the reaction was completed, the temperature was lowered to -40° C., boron tribromide (3.6eq) was slowly added, and stirring was continued at room temperature for 0.5 hours. N,N-diisopropylethylamine (5.0 eq) was added at 0°C and the reaction was continued at 120°C for 5 hours and then stopped.
  • n-butyllithium solution (3.0eq) in n-hexane was slowly added to the tert-butylbenzene solution of the precursor 9-E (1.0eq) at 0°C, stirred for 0.5 hours, and then heated to 60°C. 2 hours. After the reaction was completed, the temperature was lowered to -40° C., boron tribromide (3.6eq) was slowly added, and stirring was continued at room temperature for 0.5 hours. N,N-diisopropylethylamine (5.0 eq) was added at 0°C and the reaction was continued at 120°C for 5 hours and then stopped.
  • Examples 10 to 18 respectively provide an organic light-emitting device, as shown in FIG. 1 , the device structure includes an ITO anode 1 , a hole injection layer (HIL) 2 , a hole transport layer (HTL) 3 , and a light-emitting layer in sequence.
  • ITO anode 1 ITO anode 1
  • HIL hole injection layer
  • HTL hole transport layer
  • EML electron transport layer
  • EIL electron injection layer
  • cathode 7 the material used in the light-emitting layer is the thermally activated delayed red fluorescent material prepared in Examples 1-9.
  • the device structure of this example is as follows: ITO/HI(10nm)/HT(50nm)/Host:3wt% compound 1-F(30nm)/ET(30nm)/Liq(1nm)/Al(100nm).
  • the material of the hole injection layer is HI, and the total thickness is generally 5-20 nm, which is 10 nm in this embodiment; the material of the hole transport layer is HT, and the total thickness is generally 5-100 nm, which is 50 nm in this embodiment;
  • Host is The host material of the wide bandgap of the organic light-emitting layer, compound 1-F is the guest material and the doping concentration is 3wt%, the thickness of the organic light-emitting layer is generally 1-100nm, this embodiment is 30nm; the material of the electron transport layer is ET, the total thickness Generally, it is 5-100 nm, and in this embodiment, it is 30 nm; the electron injection layer and cathode materials are Liq (1 nm) and metal aluminum (100 nm).
  • the preparation method is the same as that of Example 10, except that the guest material of the light-emitting layer is replaced with compound 3-D.
  • the device structure is as follows: ITO/HI(10 nm)/HT(50 nm)/Host:3wt% compound 3-D(30 nm)/ET(30 nm)/Liq(1 nm)/Al(100 nm).
  • the preparation method is the same as that in Example 10, except that the guest material of the light-emitting layer is replaced with compound 4-F.
  • the device structure is as follows: ITO/HI(10nm)/HT(50nm)/Host:3wt% compound 4-F(30nm)/ET(30nm)/Liq(1nm)/Al(100nm).
  • the preparation method is the same as that of Example 10, except that the guest material of the light-emitting layer is replaced with compound 5-F.
  • the device structure is as follows: ITO/HI(10 nm)/HT(50 nm)/Host:3wt% compound 5-F(30 nm)/ET(30 nm)/Liq(1 nm)/Al(100 nm).
  • the preparation method is the same as that of Example 10, except that the guest material of the light-emitting layer is replaced by compound 6-D.
  • the device structure is as follows: ITO/HI(10nm)/HT(50nm)/Host:3wt% compound 6-D(30nm)/ET(30nm)/Liq(1nm)/Al(100nm).
  • the preparation method is the same as that of Example 10, except that the guest material of the light-emitting layer is replaced by compound 9-F.
  • the device structure is as follows: ITO/HI(10 nm)/HT(50 nm)/Host: 3 wt% compound 9-F(30 nm)/ET(30 nm)/Liq(1 nm)/Al(100 nm).
  • the preparation method is the same as that of Example 10, except that the guest material of the light-emitting layer is replaced by compound 2-F.
  • the device structure is as follows: ITO/HI(10nm)/HT(50nm)/Host:3wt% compound 2-F(30nm)/ET(30nm)/Liq(1nm)/Al(100nm).
  • the preparation method is the same as that of Example 10, except that the guest material of the light-emitting layer is replaced with compound 7-D.
  • the device structure is as follows: ITO/HI(10 nm)/HT(50 nm)/Host: 3 wt% compound 7-D(30 nm)/ET(30 nm)/Liq(1 nm)/Al(100 nm).
  • the preparation method is the same as that of Example 10, except that the guest material of the light-emitting layer is replaced by compound 8-F.
  • the device structure is as follows: ITO/HI(10nm)/HT(50nm)/Host:3wt% compound 8-F(30nm)/ET(30nm)/Liq(1nm)/Al(100nm).
  • the thermally activated delayed red light fluorescent material of the present invention includes a B- ⁇ -B linear structure; at the same time, heteroatom structural elements, heavy atoms, seven-membered rings, etc. are introduced to red-shift the fluorescence emission peak, and the fluorescence emission peak of The full width at half maximum is only 20-40nm, so that the thermally activated delayed fluorescent material of red/deep red light can be obtained; at the same time, deuterium element is introduced to improve the life stability of the device.
  • Using the thermally activated delayed red fluorescent material as a light-emitting material of an organic light-emitting device has the advantages of high light-emitting efficiency, high color purity, and small efficiency roll-off.
  • the material used in the light-emitting layer of the organic light-emitting device is a thermally activated delayed blue fluorescent material, and the general formula of the thermally activated delayed blue fluorescent material is:
  • M 101 is B
  • Ar101 is benzene ring, thiophene or selenophenol
  • X 101 is N, Bi or As
  • Ar102 and Ar103 are independently selected from thiophene, furan, benzene, benzothiophene or benzofuran
  • R 101 -R 102 independently selects benzene and substituted aryl and heteroaryl.
  • a plurality to all of the hydrogens in the structural formula of the thermally activated delayed blue fluorescent material are independently selected from deuterium.
  • R 101 -R 102 are independently selected from one of the following structural formulas:
  • the structural formula of the organic blue fluorescent material is as follows:
  • Examples 19-21 briefly describe the preparation method of the thermally activated delayed blue light fluorescent material used in the light-emitting layer of the organic light-emitting device of the present invention.
  • This embodiment provides a thermally activated delayed blue fluorescent material, which is denoted as compound 2, and the synthetic route of compound 2 is as follows:
  • the synthetic method of compound 2 specifically comprises the following steps:
  • the crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate: 5/1 (volume ratio)) to obtain compound 2, which was then purified by recrystallization from o-dichlorobenzene to obtain 0.47 g of product with a yield of 12%.
  • This embodiment provides a thermally activated delayed blue fluorescent material, which is denoted as compound 9, and the synthetic route of compound 9 is as follows:
  • the synthetic method of compound 9 specifically comprises the following steps:
  • This embodiment provides a thermally activated delayed blue fluorescent material, which is denoted as compound 4, and the synthetic route of compound 4 is as follows:
  • the synthetic method of compound 4 specifically comprises the following steps:
  • the crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate: 5/1 (volume ratio)) to obtain compound 4, which was then purified by recrystallization from o-dichlorobenzene to obtain 0.24 g of product with a yield of 6%.
  • the organic light-emitting device includes a metal cathode 101 , an electron injection layer 102 , an electron transport layer 103 , and a light-emitting layer that are sequentially stacked from top to bottom. 104.
  • This embodiment provides an organic light-emitting device based on a thermally activated delayed blue fluorescent material as a light-emitting layer, as shown in FIG. 2, including a metal cathode 101, an electron injection layer 102, an electron transport layer 103, a metal cathode 101, an electron injection layer 102, an electron transport layer 103, The light emitting layer 104 , the hole transport layer 105 , the hole injection layer 106 , the anode 107 and the glass substrate 108 .
  • the metal cathode 101 selects aluminum
  • the electron injection layer 102 is selected from lithium fluoride
  • the electron transport layer 103 selects the compound LET003 with the following structure
  • the light-emitting layer 104 is formed by co-doping a host material and a guest material, wherein the host material is selected from the compound mCBP having the following structure, the guest material is selected from compound 2, and the mass ratio of the host material to the guest material is 90:10;
  • the hole transport layer 105 is selected from the compound NPB with the following structure
  • the hole injection layer 106 selects the compound HATCN with the following structure
  • the anode 107 is indium tin oxide
  • the thermally activated delayed blue fluorescent material (compound 2) provided in this embodiment has the characteristics of narrow emission spectrum, the FWHM is only 28nm, which reflects the good color purity of the material, the external quantum efficiency of the device is 23.3%, and the brightness is 1000cd/m 2 , it still maintains 17.3%, the efficiency roll-off is lower, and the color coordinates are (0.14, 0.10).
  • This embodiment provides an organic light-emitting device based on a thermally activated delayed blue fluorescent material as a light-emitting layer, as shown in FIG. 2, including a metal cathode 101, an electron injection layer 102, an electron transport layer 103, a metal cathode 101, an electron injection layer 102, an electron transport layer 103, The light emitting layer 104 , the hole transport layer 105 , the hole injection layer 106 , the anode 107 and the glass substrate 108 .
  • the metal cathode 101 selects aluminum
  • the electron injection layer 102 is selected from lithium fluoride
  • the electron transport layer 103 selects the compound LET003 with the following structure
  • the light-emitting layer 104 is formed by co-doping the host material and the guest material, wherein the host material is selected from the compound mCBP with the following structure, the guest material is selected from the compound 9, and the mass ratio of the host material to the guest material is 90:10;
  • the hole transport layer 105 is selected from the compound NPB with the following structure
  • the hole injection layer 106 selects the compound HATCN with the following structure
  • the anode 107 is indium tin oxide
  • the thermally activated delayed blue fluorescent material (compound 9) provided in this embodiment has the characteristics of narrow emission spectrum, and the FWHM is only 26nm, which reflects the good color purity of the material.
  • the highest external quantum efficiency of the device is up to 20.5%, and the brightness is 1000cd. 15.2% is still maintained at /m2, the efficiency roll - off is lower, and the color coordinates are (0.14, 0.13).
  • This embodiment provides an organic light-emitting device based on a thermally activated delayed blue fluorescent material as a light-emitting layer, as shown in FIG. 2, including a metal cathode 101, an electron injection layer 102, an electron transport layer 103, a metal cathode 101, an electron injection layer 102, an electron transport layer 103, The light emitting layer 104 , the hole transport layer 105 , the hole injection layer 106 , the anode 107 and the glass substrate 108 .
  • the metal cathode 101 selects aluminum
  • the electron injection layer 102 is selected from lithium fluoride
  • the electron transport layer 103 selects the compound LET003 with the following structure
  • the light-emitting layer 104 is formed by co-doping the host material and the guest material, wherein the host material is selected from the compound mCBP with the following structure, the guest material is selected from the compound 4, and the mass ratio of the host material to the guest material is 90:10;
  • the hole transport layer 105 is selected from the compound NPB with the following structure
  • the hole injection layer 106 selects the compound HATCN with the following structure
  • the anode 107 is indium tin oxide
  • the thermally activated delayed blue fluorescent material (compound 4) provided in this embodiment has the characteristics of narrow emission spectrum, the FWHM is only 32nm, which reflects the good color purity of the material, the external quantum efficiency of the device is up to 26.7%, and the brightness is 1000cd/ 21.5% remains at m 2 , the efficiency roll-off is lower, and the color coordinates are (0.14, 0.12).
  • the thermally activated delayed blue light fluorescent material By using the thermally activated delayed blue light fluorescent material, the stacking between materials can be effectively improved, the triplet state quenching between molecules can be reduced, and the efficiency roll-off can be reduced; meanwhile, the unique multiple resonance structure endows the material with a narrower fluorescence emission spectrum and higher external quantum efficiency values.
  • the material used for the light-emitting layer in the organic light-emitting device is a seven-membered ring thermally activated delayed fluorescent material, and the general formula of the seven-membered ring thermally activated delayed fluorescent material is:
  • Ar 201 -Ar 204 are independently selected from benzene, thiophene, furan, pyridine or substituted above-mentioned aryl or heteroaryl
  • R 201 -R 212 are independently selected from hydrogen, deuterium, cyano or alkyl chain
  • X 101 is selected from hydrogen, deuterium, halogen, cyano, alkyl chain or benzene, thiophene, furan, carbazole, pyridine, quinoline, isoquinoline and substituted aryl or heteroaryl groups above.
  • the X 101 is one of the following groups:
  • the seven-membered ring thermally activated delayed fluorescent material is one of the following chemical structural formulas:
  • the present invention also provides a method for preparing the seven-membered ring thermally activated delayed fluorescent material, the chemical reaction process of which is as follows:
  • the raw material aromatic boronic acid and the halogenated aromatic group are dissolved in the first solvent, and the first intermediate product is obtained under the first predetermined reaction condition;
  • the first intermediate product is dissolved in the first solvent, a sufficient amount of iron powder and 3% ammonium chloride solution are added, and after heating to reflux, the solution is poured into water, filtered to obtain a filtrate, concentrated by rotary evaporation, and separated on a silica gel column to obtain the first intermediate product.
  • the first solvent is toluene
  • the second solvent is dimethyl sulfoxide
  • the third solvent is N,N-dimethylformamide
  • the fourth solvent is ethanol.
  • the first preset reaction conditions are as follows: the catalyst is 2% mol of tetrakistriphenylphosphine palladium and 5 times the equivalent of potassium carbonate; the reaction temperature is 100-110° C., and the reaction time is 24 hours.
  • the second preset reaction conditions are as follows: the catalyst is twice the equivalent of potassium tert-butoxide, the reaction temperature is 160° C., and the reaction time is 12 hours.
  • the aromatic boronic acid is Described halogenated aromatic group is a kind of in following chemical structural formula:
  • another method for preparing a seven-membered ring thermally activated delayed fluorescent material is also provided, and the chemical reaction process is as follows:
  • a substituted or unsubstituted aryl group or a heteroaryl group and the fifth intermediate product are dissolved in the first solvent, and the sixth intermediate product under the first predetermined reaction conditions;
  • the first solvent is toluene
  • the second solvent is dimethyl sulfoxide
  • the third solvent is N,N-dimethylformamide
  • the fourth solvent is ethanol.
  • the first preset reaction conditions are as follows: the catalyst is 2% mol of tetrakistriphenylphosphine palladium and 5 times the equivalent of potassium carbonate; the reaction temperature is 100-110° C., and the reaction time is 24 hours.
  • Examples 25-27 briefly describe the preparation method of the seven-membered ring thermally activated delayed fluorescent material used in the light-emitting layer of the organic light-emitting device of the present invention.
  • This embodiment provides a seven-membered ring thermally activated delayed fluorescent material, and the synthetic route of compound 231 is as follows:
  • the synthetic method of described compound 231 specifically comprises the following steps:
  • Synthesis of intermediate 1 take a 500mL round-bottomed flask, connect a spherical condenser, dry and fill with nitrogen, add raw material 1 (2.52 g, 10 mmol), raw material 2 (2.47 g, 12 mmol), tetrakistriphenylphosphine palladium, respectively (231.2 mg, 0.2 mmol), 20 mL of 2 mol/L potassium carbonate aqueous solution, 200 mL of toluene.
  • Synthesis of compound 231 take a 100mL Schlenk bottle, add Intermediate 2 (3.44g, 5mmol), 50mL tert-butylbenzene, freeze and pump three times with liquid nitrogen, and slowly add 2.4mL n-butyllithium (6mmol, 2.5mol) at 0 degrees /L n-hexane), slowly heated to 60 degrees and continued to react for 4 hours. Cool to -42 degrees, slowly add boron tribromide (0.68 mL, 7 mmol), and slowly warm to room temperature to continue the reaction for 2 hours.
  • N,N-diisopropylethylamine (1.65 mL, 10 mmol) was slowly added under an ice-water bath, and the mixture was gradually heated to 120°C and reacted for 24 hours.
  • the reaction solution was cooled to room temperature, washed three times with sodium acetate solution, the organic phase was collected and dried with anhydrous magnesium sulfate, the crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate was 10/1 (volume ratio)) to obtain compound 231 (0.62 g, 20% yield).
  • This embodiment provides a seven-membered ring thermally activated delayed fluorescent material, and the synthetic route of compound 253 is as follows:
  • the synthetic method of compound 253 specifically comprises the following steps:
  • Synthesis of compound 253 take a 100mL Schlenk bottle, add Intermediate 6 (3.85g, 5mmol), 50mL tert-butylbenzene, freeze three times with liquid nitrogen, slowly add 2.4mL n-butyllithium (6mmol, 2.5mol) at 0 degrees /L n-hexane), slowly heated to 60 degrees and continued to react for 4 hours. Cool to -42 degrees, slowly add boron tribromide (0.68 mL, 7 mmol), and slowly warm to room temperature to continue the reaction for 2 hours.
  • N,N-diisopropylethylamine (1.65 mL, 10 mmol) was slowly added under an ice-water bath, and the mixture was gradually heated to 120°C and reacted for 24 hours.
  • the reaction solution was cooled to room temperature, washed three times with sodium acetate solution, the organic phase was collected and dried with anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate was 10/1 (volume ratio)) to obtain compound 253 (0.67 g, 18% yield).
  • This embodiment provides a seven-membered ring thermally activated delayed fluorescent material, and the synthetic route of compound 298 is as follows:
  • the synthetic method of compound 298 specifically comprises the following steps:
  • the present invention provides the following Examples 28-30, respectively providing an organic light-emitting device, comprising a light-emitting layer, and the light-emitting layer uses The material is the seven-membered ring thermally activated delayed fluorescent material prepared in Examples 25-27.
  • the present invention provides an organic light-emitting device based on a seven-membered ring thermally activated delayed fluorescent material as a light-emitting layer.
  • a metal cathode 101 As shown in FIG. 2, a metal cathode 101, an electron injection layer 102, an electron transport layer 103, a light-emitting layer 104 , hole transport layer 105 , hole injection layer 106 , anode 107 and glass substrate 108 .
  • the metal cathode 101 is selected from aluminum
  • the electron injection layer 102 is selected from lithium fluoride
  • the electron transport layer 103 is selected from the following structure
  • the compound LET003; the light-emitting layer 104 is formed by co-doping the host material and the guest material, wherein the host material is selected to have the following structure
  • the compound mCBP, the guest material is compound 298
  • the mass ratio of the host material and the guest material doping is 90:10;
  • the hole transport layer 105 is selected to have the following structure
  • the hole injection layer 106 is selected to have the following structure The compound HATCN; the anode 107 selects indium tin oxide.
  • An organic electroluminescence device is provided, which is different from the organic electroluminescence device provided in Example 28 in that compound 231 is selected as the material of the light-emitting layer.
  • An organic electroluminescent device is provided, which is different from the organic electroluminescent device provided in Example 28 in that compound 253 is selected as the material of the light-emitting layer.
  • the thermal stability test was carried out on the seven-membered ring thermally activated delayed fluorescent material prepared in Example 28. The results are shown in Figure 3. It can be seen from Figure 3 that the decomposition temperature of the seven-membered ring thermally activated delayed fluorescent material is 415 degrees. , indicating that the seven-membered ring thermally activated delayed fluorescent material has excellent thermal stability.
  • the emission spectrum of the seven-membered ring thermally activated delayed fluorescent material prepared in Example 28 is tested, and the results are shown in Figure 4. It can be seen from Figure 4 that the emission spectrum of the seven-membered ring thermally activated delayed fluorescent material is only 28nm , indicating that the seven-membered ring thermally activated delayed fluorescent material has the characteristics of narrow emission spectrum, which reflects the good color purity of the material.
  • the introduction of the seven-membered ring can effectively improve the stacking between materials, reduce the triplet quenching of the molecules, and reduce the efficiency roll-off , improve the stability and working life of the device; at the same time, the unique boron-nitrogen multiple resonance structure endows the material with a narrow fluorescence emission spectrum and a high external quantum efficiency value.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un dispositif électroluminescent organique comprenant un matériau à fluorescence retardée activée thermiquement utilisé en tant que matériau de couche électroluminescente. Le matériau à fluorescence retardée activé thermiquement comprend l'un parmi un matériau à fluorescence retardée activée thermiquement à lumière rouge, un matériau à fluorescence retardée activée thermiquement à lumière bleue, ou un matériau à fluorescence retardée activée thermiquement cyclique à sept chaînons. La formule générale du matériau à fluorescence retardée activée thermiquement à lumière rouge est : aa ; la formule générale du matériau à fluorescence retardée activée thermiquement à lumière bleue est : bb ; la formule générale du matériau à fluorescence retardée activée thermiquement cyclique à sept chaînons est : cc.
PCT/CN2022/076179 2021-03-01 2022-02-14 Dispositif électroluminescent organique comprenant un matériau à fluorescence retardée activée thermiquement utilisé en tant que matériau de couche électroluminescente WO2022183900A1 (fr)

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CN202110224292.7 2021-03-01
CN202110224292.7A CN113072569A (zh) 2021-03-01 2021-03-01 一种热激活延迟蓝色荧光材料与有机发光二极管
CN202110224872.6 2021-03-01
CN202110238720.1A CN113072571B (zh) 2021-03-04 2021-03-04 一种七元环热激活延迟荧光材料及其制备方法、有机发光器件
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