WO2020199325A1 - Matériau à fluorescence retardée activé thermiquement, procédé de préparation correspondant, et dispositif électroluminescent - Google Patents

Matériau à fluorescence retardée activé thermiquement, procédé de préparation correspondant, et dispositif électroluminescent Download PDF

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Publication number
WO2020199325A1
WO2020199325A1 PCT/CN2019/087932 CN2019087932W WO2020199325A1 WO 2020199325 A1 WO2020199325 A1 WO 2020199325A1 CN 2019087932 W CN2019087932 W CN 2019087932W WO 2020199325 A1 WO2020199325 A1 WO 2020199325A1
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solution
thermally activated
fluorescent material
activated delayed
delayed fluorescent
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PCT/CN2019/087932
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English (en)
Chinese (zh)
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王彦杰
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武汉华星光电半导体显示技术有限公司
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Publication of WO2020199325A1 publication Critical patent/WO2020199325A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero 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

Definitions

  • the invention relates to the field of display technology, in particular to a thermally activated delayed fluorescent material, a preparation method thereof, and an electroluminescent device.
  • OLEDs Organic light-emitting diodes
  • OLEDs due to active light emission, large viewing angle, fast response speed, wide temperature adaptation range, low driving voltage, low power consumption, high brightness, simple production process, light and thin, and can
  • the advantages of flexible display and other advantages have shown great application prospects in the field of OLED display and lighting, attracting the attention of scientific researchers and companies.
  • Samsung and LG have implemented OLEDs in mobile phones.
  • the usual luminescent layer material consists of host and guest luminescent materials, and the luminous efficiency and lifetime of luminescent materials are two important indicators of the quality of luminescent materials.
  • Early OLED light-emitting materials were traditional fluorescent materials.
  • the ratio of singlet and triplet excitons is 1:3, while traditional fluorescent materials can only use singlet excitons to emit light. Therefore, traditional fluorescent
  • the OLED theoretical internal quantum efficiency of the material is 25%. Due to the spin-orbit coupling effect of heavy atoms, metal complex phosphorescent materials can achieve 100% utilization of singlet excitons and triplet excitons; and are now also used in red and green OLED display devices .
  • phosphorescent materials usually use heavy metals such as iridium, platinum, osmium and other precious metals, which are not only costly, but also highly toxic. In addition, efficient and long-life phosphorescent metal complex materials are still a great challenge.
  • the present invention provides a thermally activated delayed fluorescent material and a preparation method thereof, and an electroluminescent device.
  • the structure of the thermally activated delayed fluorescent material is DAA type, where D is an electron donor and A is an electron acceptor .
  • D is an electron donor
  • A is an electron acceptor
  • the present invention provides a thermally activated delayed fluorescent material, which has the following general structural formula:
  • D is an electron donor
  • A is an electron acceptor
  • the electron donor includes one of the following structures:
  • the electron acceptor includes at least one of the following structures:
  • the method for preparing the thermally activated delayed fluorescent material includes the following steps: preparing a format reagent, and placing the format reagent in a first three-necked flask; placing the first reactant and tetrahydrofuran A first solution is obtained from the first reaction flask, wherein the first reactant has the structure of 4-bromophenyl and electron acceptor; the first solution is dropped into the first reaction flask to perform the Grignard reaction , Get the second solution, and stir at room temperature for 1-3 hours, then place the second solution in a dry ice/acetone bath; place trichlorotriazine and tetrahydrofuran in the second reaction flask to obtain the third solution; The second solution was added dropwise to the third solution, and reacted for 2 hours at a temperature of -78°C, then slowly raised to room temperature, and allowed to stand for 12 hours to 24 hours to obtain the fourth solution; the fourth solution was added to distilled water , And extract with
  • the format reagent includes tetrahydrofuran, magnesium and iodine.
  • the step of performing the Grignard reaction includes heating the first three-necked flask to initiate the Grignard reaction at the beginning of the Grignard reaction.
  • the first three The mouth flask was placed in an ice water bath to adjust the reaction temperature.
  • the present invention also provides an electroluminescent device, which includes the thermally activated delayed fluorescent material.
  • the electroluminescent device includes a first electrode; an electron injection layer provided on the first electrode; a hole transport layer provided on the electron injection layer; a light emitting layer, It is arranged on the hole transport layer, and the material used for the light emitting layer includes the thermally activated delayed fluorescent material; the electron transport layer is arranged on the light emitting layer; and the second electrode is arranged on the electron transport layer.
  • the first electrode is an anode, and the material used is indium tin oxide; the second electrode is a cathode, and the material used is one of lithium fluoride or aluminum.
  • the material used for the electron transport layer is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • the material used for the hole transport layer is 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline].
  • the thermally activated delayed fluorescent material of the present invention has an electron acceptor.
  • the electron acceptor effectively increases the electron-withdrawing ability and rigidity of the thermally activated delayed fluorescent material, and can effectively inhibit the non-radiative transition rate, thereby improving the thermally activated delayed fluorescent material.
  • Photoluminescence quantum yield (PLQY) at the same time, it can reduce the electron cloud overlap between the highest occupied molecular orbital (HOMO) and the lowest occupied molecular orbital (LUMO), so as to obtain a smaller minimum singlet and triplet energy level difference ( ⁇ EST), in addition, you can also adjust the emission spectrum of the molecule.
  • the preparation method of the thermally activated delayed fluorescent material of the present invention can effectively improve the synthesis efficiency.
  • the electroluminescent device of the present invention which has the thermally activated delayed fluorescent material of the present invention, can effectively improve the luminous efficiency.
  • Fig. 1 is a fluorescence spectrum diagram of a thermally activated delayed fluorescent material prepared by a preparation method in an embodiment of the present invention.
  • Fig. 2 is a structural diagram of an electroluminescent device in an embodiment of the present invention.
  • the thermally activated delayed fluorescent material of the present invention has the following general structural formula:
  • D is an electron donor
  • A is an electron acceptor
  • the electron donor includes one of the following structures:
  • the electron acceptor includes at least one of the following structures:
  • the molecular structures of the thermally activated delayed fluorescent material in this embodiment are as follows:
  • thermally activated delayed fluorescent material will be further explained below in conjunction with the preparation method of the thermally activated delayed fluorescent material of the present invention.
  • the preparation method of the thermally activated delayed fluorescent material includes the following steps:
  • the format reagent includes tetrahydrofuran, magnesium and iodine.
  • the volume of tetrahydrofuran is 30 ml, and the amount of magnesium is 15 mmol.
  • the first reactant and tetrahydrofuran are placed in the first reaction flask to obtain the first solution, wherein the first reactant has the structure of 4-bromophenyl and electron acceptor.
  • the volume of tetrahydrofuran is 30 ml, and the amount of the substance of the first reactant is 10 mmol; the structural formula of the first reactant is:
  • the first solution was added dropwise to the first reaction flask, and the Grignard reaction was performed to obtain the second solution, which was stirred at room temperature for 1-3 hours, and then the second solution was placed in a dry ice/acetone bath.
  • the first three-necked flask can be heated at the beginning of the Grignard reaction to initiate the Grignard reaction.
  • the first three-necked flask is placed Adjust the reaction temperature in an ice water bath.
  • the second solution was added dropwise to the third solution and reacted for 2 hours at a temperature of -78°C, then slowly raised to room temperature, and allowed to stand for 12 hours to 24 hours to obtain a fourth solution.
  • the fourth solution was added to distilled water and extracted with dichloromethane several times. After each extraction, it was washed with distilled water to obtain the first extract; the first extract was dried with anhydrous sodium sulfate, filtered, and spin-dried. Then use 200-300 mesh silica gel for column chromatography, and rinse with eluent to obtain the intermediate. In this step, the volume of distilled water is 100ml. In this example, the yield of the intermediate is at least 78%.
  • the amount of the intermediate substance is 5 mmol; the amount of pyridine-3-phenylboronic acid is 11 mmol; the volume of toluene is 8 ml; the amount of tetrakis(triphenylphosphorus) palladium is 0.2 mmol.
  • the fifth solution was added to distilled water, and extracted with dichloromethane several times, and washed with distilled water after each extraction to obtain a second extract.
  • the second extract was dried with anhydrous sodium sulfate, filtered, and spin-dried, and then column chromatography was performed with 200-300 mesh silica gel and eluted with eluent to obtain the thermally activated delayed fluorescent material.
  • the production rate of the thermally activated delayed fluorescent material is at least 84%.
  • the structural formula of the thermally activated delayed fluorescent material is:
  • the thermally activated delayed fluorescent material By preparing the thermally activated delayed fluorescent material by the preparation method of this embodiment, the thermally activated delayed fluorescent material can be effectively synthesized, and the synthesis efficiency can be improved.
  • the thermally activated delayed fluorescent material obtained by the preparation method of this embodiment is subjected to spectral experiments and photophysical data detection. Obtain the fluorescence spectrum shown in Figure 1 and the photophysical data shown in Table 1.
  • Table 1 shows the photophysical data of the thermally activated delayed fluorescent material of the present invention.
  • the effective wavelength range of the thermally activated delayed fluorescent material of the present invention is between 500-700, and therefore, the emission spectrum of the molecule can be adjusted within this range. It can be seen from Table 1 that the thermally activated delayed fluorescent material of the present invention has a smaller minimum singlet state and triplet energy difference ( ⁇ E ST ).
  • the present invention also provides an electroluminescent device, which includes the thermally activated delayed fluorescent material.
  • the electroluminescent device includes a first electrode 1, an electron injection layer 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a second electrode 6.
  • the electron injection layer 2 is provided on the first electrode 1;
  • the hole transport layer 3 is provided on the electron injection layer 2;
  • the light emitting layer 4 is provided on the hole transport layer 3
  • the material used for the light-emitting layer 4 includes the thermally activated delayed fluorescent material;
  • the electron transport layer 5 is provided on the light-emitting layer 4;
  • the second electrode 6 is provided on the electron transport layer 5.
  • the first electrode 1 is an anode, and the material used is indium tin oxide; the second electrode 6 is a cathode, and the material used is one of lithium fluoride or aluminum.
  • the material used for the electron transport layer 5 is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene; the hole transport layer 3
  • the material used is 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline].
  • the electroluminescent device 10 of the present invention adopts the thermally activated delayed fluorescent material in the luminescent layer 4, which effectively improves the luminous efficiency of the electroluminescent device 10.

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

Abstract

L'invention concerne un matériau à fluorescence retardée activé thermiquement, comprenant un noyau de triazinyle, un donneur d'électrons et un accepteur d'électrons liés au noyau et capables d'inhiber un taux de transition non radiative. L'invention concerne en outre un dispositif électroluminescent qui comprend le matériau à fluorescence retardée activé thermiquement, et qui peut améliorer de manière efficace l'efficacité d'émission de lumière.
PCT/CN2019/087932 2019-03-29 2019-05-22 Matériau à fluorescence retardée activé thermiquement, procédé de préparation correspondant, et dispositif électroluminescent WO2020199325A1 (fr)

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CN201910250391.5 2019-03-29
CN201910250391.5A CN109879857A (zh) 2019-03-29 2019-03-29 热激活延迟荧光材料及其制备方法、电致发光器件

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CN110015994A (zh) * 2019-04-29 2019-07-16 武汉华星光电半导体显示技术有限公司 热活化延迟荧光材料及其制备方法、显示装置
CN110372701A (zh) * 2019-07-09 2019-10-25 武汉华星光电半导体显示技术有限公司 一种热活化延迟荧光分子及其制备方法、电致热激活延迟荧光器件

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CN104592194A (zh) * 2015-01-04 2015-05-06 华南理工大学 一种噻蒽氧化物-芳香胺有机发光小分子及制备与应用
EP3315581B1 (fr) * 2016-11-01 2019-01-02 Cynora Gmbh Molécules organiques, en particulier destinées à être utilisées dans des composants optoélectroniques organiques

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CN103539751A (zh) * 2013-10-17 2014-01-29 南京大学 一类均三嗪衍生物及其在有机电致发光器件中的应用
US20170148999A1 (en) * 2014-05-02 2017-05-25 Samsung Display Co., Ltd. Organic light-emitting device
CN108239072A (zh) * 2016-12-27 2018-07-03 江苏三月光电科技有限公司 一种三嗪衍生物及其在有机电致发光器件上的应用

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