WO2022120945A1 - 空穴传输材料及其制备方法、电致发光器件 - Google Patents

空穴传输材料及其制备方法、电致发光器件 Download PDF

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WO2022120945A1
WO2022120945A1 PCT/CN2020/138351 CN2020138351W WO2022120945A1 WO 2022120945 A1 WO2022120945 A1 WO 2022120945A1 CN 2020138351 W CN2020138351 W CN 2020138351W WO 2022120945 A1 WO2022120945 A1 WO 2022120945A1
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compound
hole transport
transport material
solution
layer
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王彦杰
罗佳佳
白科研
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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    • H—ELECTRICITY
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    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/93—Spiro compounds
    • C07C2603/95—Spiro compounds containing "not free" spiro atoms
    • C07C2603/96—Spiro compounds containing "not free" spiro atoms containing at least one ring with less than six members
    • C07C2603/97—Spiro compounds containing "not free" spiro atoms containing at least one ring with less than six members containing five-membered rings
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to the technical field of display, in particular to a hole transport material, a preparation method thereof, and an electroluminescence device.
  • Organic electronic devices refer to devices composed of an anode, a cathode and an organic layer sandwiched between the anode and the cathode, including organic light-emitting diodes, organic solar cells, organic semiconductors, organic crystals, and the like. Its working principle is to apply an external voltage on the electrode, inject holes and electrons into the organic layer to form excitons, thereby radiating light (organic light-emitting diodes); or the external light source is absorbed by organic materials to form excitons, and the excitons are separated into empty spaces. Holes and electrons are transferred to electrodes and stored (organic solar cells).
  • the organic layers of organic electronic devices are all one or more layers of organic materials, which are hole injection or transport materials, electron injection or transport materials, or light-emitting materials, respectively. Among them, these different organic materials all operate based on similar principles in different organic electronic devices:
  • An organic light-emitting diode is a phenomenon that converts electrical energy into light energy, and its structure is usually an anode, a cathode, and multiple layers of organic materials interposed therebetween.
  • the organic material layers are classified into hole injection materials, hole transport materials, electron injection materials, electron transport materials, and light-emitting materials according to functions.
  • luminescent materials are further classified into luminescent materials such as blue, sky blue, green, yellow, red, and deep red according to the luminescent color.
  • the evaluation indicators of organic light-emitting diodes are mainly voltage, efficiency and life. How to develop low-voltage, high-efficiency and long-life electroluminescent devices has always been the goal pursued by the R&D and commercial circles, which requires electrons/holes with high mobility. Injection and transport materials, high-efficiency light-emitting materials, and efficient balance of electrons and holes in devices.
  • the type of vapor deposition (sublimation type or fusion type), decomposition temperature, glass transition temperature, outgassing phenomenon, etc. of the material must also be considered.
  • thicker hole transport materials need to be evaporated. The sublimation material in this material will seriously affect the uniformity of mass production film thickness, so the development of molten hole transport materials has also become an important direction.
  • the purpose of the present invention is to provide a hole transport material, a preparation method thereof, and a display device, so as to solve the problems in the prior art that the vapor-deposited hole transport material is unstable and unfavorable for mass production when preparing a display device.
  • the present invention provides a hole transport material, the main chain of the molecular structure of the hole transport material has a spiro anthracene fluorene structure, and its molecular structure is as follows:
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 contain at least one aryl group or heteroaryl group;
  • R is a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 group At least one of heteroaryl;
  • R 1 -R 6 are respectively at least one of hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 aryl or C 1 -C 60 heteroaryl ;
  • a, b, c and d are integers less than 5.
  • molecular structure of Ar 1 , Ar 2 , Ar 3 and Ar 4 is one of the following structures:
  • R 7 -R 10 and the L are a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the R 3 -R 6 are respectively one of hydrogen or deuterium; when a, b, c and d are 1-4, the R 3 -R 6 is respectively a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the molecular structural formula of the hole transport material is:
  • R is a kind of in following group structure:
  • the present invention also provides a method for preparing a hole transport material, which includes the following steps:
  • the molecular structure of the first compound includes the following structures:
  • R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group;
  • X is one of halogen elements.
  • the first compound and the second compound are placed in a reaction vessel for deoxygenation treatment.
  • the catalyst is added to the reaction vessel, and the first solution is obtained by fully reacting at a temperature of 50°C-150°C.
  • the molecular structure of the second compound contains at least one aryl or heteroaryl group.
  • Purifying the first target substance using the eluent, purifying the first solution by silica gel column chromatography to obtain the hole transport material.
  • step of preparing the first compound also includes the following steps:
  • the molecular structure of the third compound includes the following structures:
  • Synthesis of the second target placing the third compound, concentrated hydrochloric acid and glacial acetic acid in a reaction vessel, fully reacting at a temperature of 50-100 ° C and adding sodium bicarbonate to obtain a second solution, the second solution shown contains the second target.
  • Extracting the second target substance adding dichloromethane to the second solution for extraction to obtain the second target substance.
  • Purifying the second target substance using the eluent, purify the second target substance by silica gel column chromatography to obtain the first compound.
  • step of preparing the third compound includes the following steps:
  • the fourth compound is dissolved in tetrahydrofuran, and butyllithium is added to obtain a reaction solution after the reaction.
  • the fifth compound is dissolved in tetrahydrofuran and added dropwise to the reaction solution, and the third solution is obtained after sufficient reaction. The liquid in the third solution is removed to obtain the third compound.
  • the molecular structure of the fourth compound includes the following structures:
  • Y in the molecular structure of the fourth compound is a halogen element.
  • the fifth compound has an anthracene structure in its molecular structural formula.
  • the present invention also provides an electroluminescent device, which includes a substrate layer, a first electrode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a second electrode.
  • the first electrode is disposed on the substrate layer.
  • the hole injection layer is disposed on the first electrode.
  • the hole transport layer is provided on the hole injection layer.
  • the light-emitting layer is provided on the hole transport layer.
  • the electron transport layer is provided on the light emitting layer.
  • the electron injection layer is provided on the electron transport layer.
  • the second electrode is disposed on the electron injection layer.
  • the hole injection layer and/or the hole transport layer has the above hole transport material.
  • the advantages of the present invention are: in the hole transport material of the present invention, the aromatic amine in the molecular structure can effectively improve the hole injection and transport performance of the organic material, thereby improving the balance of electrons and holes in the electroluminescent device, and achieving lower voltage and higher efficiency.
  • the introduction of an alkyl, aryl or heteroaryl structure at the 4-position of fluorene can adjust the evaporation temperature, melting or sublimation characteristics, mobility, etc. of the material, which is beneficial to the stability of mass production evaporation and improves the performance of the device.
  • FIG. 1 is a schematic diagram of a layered structure of an electroluminescent device in an application example of the present invention.
  • hole injection layer 3 hole transport layer 4;
  • Electron blocking layer 5 Light emitting layer 6;
  • Electron transport layer 7 Electron injection layer 8;
  • the second electrode 9 The second electrode 9 .
  • the embodiment of the present invention provides a hole transport material, the main chain in the molecular structural formula of the hole transport material is a spiroanthracene fluorene structure, and its molecular structural formula is:
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 contain at least one aryl group or heteroaryl group;
  • R is a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 group At least one of heteroaryl;
  • R 1 -R 6 are respectively at least one of hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 aryl or C 1 -C 60 heteroaryl ;
  • a, b, c and d are integers less than 5.
  • the molecular structure of the Ar1 is:
  • R 7 and R 8 are an aryl structure or a heteroaryl structure.
  • the ad is all 0, and R 1 -R 6 are all hydrogen bonds.
  • the molecular structural formula of the hole transport material is:
  • the embodiments of the present invention also provide a method for preparing the above hole transport material, which includes the following preparation steps:
  • Step S10) preparing a third compound includes the following structures:
  • X in the molecular structural formula is a halogen element
  • R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the step of preparing the third compound includes:
  • the fourth compound (11 mmol, 3.43 g) and tetrahydrofuran (20 mL) were added to a reaction vessel, and the reaction vessel was placed under an argon atmosphere and stirred to dissolve.
  • the reaction vessel was placed in an environment with a temperature of -60°C to -90°C, preferably -78°C, and butyllithium (7.5mL, 1.6M) was slowly added dropwise, and the reaction was maintained for 1 hour to obtain a reaction solution.
  • the molecular structure of the fourth compound includes the following structures:
  • Both X and Y in this molecular structural formula are halogen elements, and R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the fifth compound (10 mmol, 2.22 g) was dissolved in tetrahydrofuran (20 mL), and also slowly dropped into the reaction solution at a temperature of -60°C to -90°C, preferably -78°C. After the dropwise addition, the reaction solution was warmed to room temperature and reacted for 12 hours. After the reaction is completed, an appropriate amount of ammonium chloride is added to quench the reaction to obtain the third solution. The liquid in the third solution is removed by rotation to obtain the third compound.
  • the molecular structural formula of the fifth compound has an anthracene structure.
  • the fourth compound is 1-bromo-3'-chloro-4-phenylbiphenyl
  • the fifth compound is 9,9-dimethylanthrone.
  • the preparation scheme of the third compound is shown in formula 1:
  • Step S20) preparing a first compound includes the following structures:
  • X in the molecular structural formula is a halogen element
  • R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the steps of preparing the first compound include the following steps:
  • Step S21) Synthesis of the second target substance: the third compound obtained in step S10 is placed in a reaction vessel, and concentrated hydrochloric acid (5mL) and glacial acetic acid (15mL) are added, and the temperature is 50-100 °C, preferably It was made to react under the environment of 80 degreeC for 24 hours, and the 2nd solution was obtained.
  • the second solution has the second target substance generated by the reaction.
  • Step S22) Extracting the second target: after cooling the second solution to room temperature, pour it into ice water, add aqueous sodium bicarbonate (1M), and neutralize the acidic solution in the second solution by sodium bicarbonate . Then, the extraction was repeated three times using dichloromethane, and the extract obtained by the three extractions was washed three times with water, followed by drying using anhydrous sodium sulfate. The dried extract was filtered and concentrated to obtain the second target.
  • Step S23) Purifying the second target substance: using petroleum ether and dichloromethane (volume ratio of 4:1) as the eluent, the organic matter is separated and purified by a 200-300 mesh silica gel chromatography column to obtain about 4.31g of The first compound in 92% yield.
  • Step S30) Synthesize the first target compound: put the first compound (2.35g, 5mmol), the second compound (1.61g, 5mmol), t-BuONa (8mmol, 0.76g) and toluene (30mL) in a reaction In a container, nitrogen was introduced for deoxygenation. Then add tris(dibenzylideneacetone)dipalladium (0.09mmol, 81mg) and tri-tert-butylphosphine tetrafluoroborate (0.92mmol, 0.24g), at a temperature of 100°C-150°C, preferably 110°C Under sufficient reaction, the first solution is obtained.
  • the first solution has a first target compound synthesized by reaction.
  • the molecular structure of the second compound contains at least one aryl group or heteroaryl group.
  • Step S40) Purifying the first target substance: after cooling the first solution to room temperature, concentrating the first solution to obtain the above-mentioned first target substance. Then, 200-300 mesh silica gel column chromatography is used to separate and purify the organic matter in the first target to obtain about 3.21 g of hole transport material with a yield of 85%.
  • the second compound is di-4-phenyl-aniline.
  • the preparation process of the hole transport material is shown in formula 3
  • the introduced aromatic amine can effectively improve the hole injection and transport performance of the organic material, thereby improving the balance of electrons and holes in the electroluminescent device, and achieving a lower voltage and higher efficiency.
  • the introduction of an alkyl, aryl or heteroaryl structure at the 4-position of fluorene can adjust the evaporation temperature, melting or sublimation characteristics, mobility, etc. of the material, thereby facilitating the stability of mass production evaporation and improving the performance of the device.
  • the embodiment of the present invention provides a hole transport material, the main chain in the molecular structural formula of the hole transport material is a spiroanthracene fluorene structure, and its molecular structural formula is:
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 contain at least one aryl group or heteroaryl group;
  • R is a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 group At least one of heteroaryl;
  • R 1 -R 6 are respectively at least one of hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 aryl or C 1 -C 60 heteroaryl ;
  • a, b, c and d are integers less than 5.
  • the molecular structure of the Ar1 is:
  • R 7 and R 8 are an aryl structure or a heteroaryl structure.
  • the ad is all 0, and R 1 -R 6 are all hydrogen bonds.
  • the molecular structural formula of the hole transport material is:
  • the embodiments of the present invention also provide a method for preparing the above hole transport material, which includes the following preparation steps:
  • Step S10) preparing a third compound includes the following structures:
  • X in the molecular structural formula is a halogen element
  • R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the step of preparing the third compound includes:
  • the fourth compound (11 mmol, 3.55 g) and tetrahydrofuran (20 mL) were added to a reaction vessel, and the reaction vessel was placed under an argon atmosphere and stirred to dissolve.
  • the reaction vessel was placed in an environment with a temperature of -60°C to -90°C, preferably -78°C, and butyllithium (7.5mL, 1.6M) was slowly added dropwise, and the reaction was maintained for 1 hour to obtain a reaction solution.
  • the molecular structure of the fourth compound includes the following structures:
  • Both X and Y in this molecular structural formula are halogen elements, and R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the fifth compound (10 mmol, 2.22 g) was dissolved in tetrahydrofuran (20 mL), and also slowly dropped into the reaction solution at a temperature of -60°C to -90°C, preferably -78°C. After the dropwise addition, the reaction solution was warmed to room temperature and reacted for 12 hours. After the reaction is completed, an appropriate amount of ammonium chloride is added to quench the reaction to obtain the third solution. The liquid in the third solution is removed by rotation to obtain the third compound.
  • the molecular structural formula of the fifth compound has an anthracene structure.
  • the fourth compound is 1-bromo-3'-chloro-4-tert-butylbiphenyl
  • the fifth compound is 9,9-dimethylanthrone.
  • the preparation scheme of the third compound is shown in formula 4:
  • Step S20) preparing a first compound includes the following structures:
  • X in the molecular structural formula is a halogen element
  • R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the steps of preparing the first compound include the following steps:
  • Step S21) Synthesis of the second target substance: the third compound obtained in step S10 is placed in a reaction vessel, and concentrated hydrochloric acid (5mL) and glacial acetic acid (15mL) are added, and the temperature is 50-100 °C, preferably It was made to react under the environment of 80 degreeC for 24 hours, and the 2nd solution was obtained.
  • the second solution has the second target substance generated by the reaction.
  • Step S22) Extracting the second target: after cooling the second solution to room temperature, pour it into ice water, add aqueous sodium bicarbonate (1M), and neutralize the acidic solution in the second solution by sodium bicarbonate . Then, the extraction was repeated three times using dichloromethane, and the extract obtained by the three extractions was washed three times with water, followed by drying using anhydrous sodium sulfate. The dried extract was filtered and concentrated to obtain the second target.
  • Step S23) Purifying the second target substance: using petroleum ether and dichloromethane (volume ratio of 5:1) as the eluent, the organic matter is separated and purified by a 200-300 mesh silica gel chromatography column to obtain about 3.95g of The first compound in 88% yield.
  • Step S30) Synthesize the first target compound: put the first compound (2.25g, 5mmol), the second compound (1.61g, 5mmol), t-BuONa (8mmol, 0.76g) and toluene (30mL) in a reaction In a container, nitrogen was introduced for deoxygenation. Then add tris(dibenzylideneacetone)dipalladium (0.09mmol, 81mg) and tri-tert-butylphosphine tetrafluoroborate (0.92mmol, 0.24g), at a temperature of 100°C-130°C, preferably 110°C Under sufficient reaction, the first solution is obtained.
  • the first solution has a first target compound synthesized by reaction.
  • the molecular structure of the second compound contains at least one aryl group or heteroaryl group.
  • Step S40) Purifying the first target substance: after cooling the first solution to room temperature, concentrating the first solution to obtain the above-mentioned first target substance. Then, 200-300 mesh silica gel column chromatography is used to separate and purify the organic matter in the first target to obtain about 3.16 g of hole transport material with a yield of 86%.
  • the second compound is di-4-phenyl-aniline.
  • the preparation process of the hole transport material is shown in formula 6
  • the introduced aromatic amine can effectively improve the hole injection and transport performance of the organic material, thereby improving the balance of electrons and holes in the electroluminescent device, and achieving a lower voltage and higher efficiency.
  • the introduction of an alkyl, aryl or heteroaryl structure at the 4-position of fluorene can adjust the evaporation temperature, melting or sublimation characteristics, mobility, etc. of the material, which is beneficial to the stability of mass production evaporation and improves the performance of the device.
  • the embodiment of the present invention provides a hole transport material, the main chain in the molecular structural formula of the hole transport material is a spiroanthracene fluorene structure, and its molecular structural formula is:
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 contain at least one aryl group or heteroaryl group;
  • R is a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 group At least one of heteroaryl;
  • R 1 -R 6 are respectively at least one of hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 aryl or C 1 -C 60 heteroaryl ;
  • a, b, c and d are integers less than 5.
  • the molecular structure of Ar1 is:
  • R 9 and R 10 are aryl structure or heteroaryl structure, and the structure of L is:
  • the structure of the R is:
  • the ad is all 0, and R 1 -R 6 are all hydrogen bonds.
  • the molecular structural formula of the hole transport material is:
  • the embodiments of the present invention also provide a method for preparing the above hole transport material, which includes the following preparation steps:
  • Step S10) preparing a third compound includes the following structures:
  • X in the molecular structural formula is a halogen element
  • R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the step of preparing the third compound includes:
  • the fourth compound (11 mmol, 3.43 g) and tetrahydrofuran (20 mL) were added to a reaction vessel, and the reaction vessel was placed under an argon atmosphere and stirred to dissolve.
  • the reaction vessel was placed in an environment with a temperature of -60°C to -90°C, preferably -78°C, and butyllithium (7.5mL, 1.6M) was slowly added dropwise, and the reaction was maintained for 1 hour to obtain a reaction solution.
  • the molecular structure of the fourth compound includes the following structures:
  • Both X and Y in this molecular structural formula are halogen elements, and R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the fifth compound (10 mmol, 2.22 g) was dissolved in tetrahydrofuran (20 mL), and also slowly dropped into the reaction solution at a temperature of -60°C to -90°C, preferably -78°C. After the dropwise addition, the reaction solution was warmed to room temperature and reacted for 12 hours. After the reaction, an appropriate amount of ammonium chloride was added to quench the reaction to obtain the third solution. The liquid in the third solution is removed by rotation to obtain the third compound.
  • the molecular structural formula of the fifth compound has an anthracene structure.
  • the fourth compound is 1-bromo-3'-chloro-4-phenylbiphenyl
  • the fifth compound is 9,9-dimethylanthrone.
  • the preparation scheme of the third compound is shown in formula 7:
  • Step S20) preparing a first compound includes the following structures:
  • X in the molecular structural formula is a halogen element
  • R is at least one of a C 1 -C 60 alkyl group, a C 1 -C 60 aryl group or a C 1 -C 60 heteroaryl group.
  • the steps of preparing the first compound include the following steps:
  • Step S21) Synthesis of the second target substance: the third compound obtained in step S10 is placed in a reaction vessel, and concentrated hydrochloric acid (5mL) and glacial acetic acid (15mL) are added, and the temperature is 50-100 °C, preferably It was made to react under the environment of 80 degreeC for 24 hours, and the 2nd solution was obtained.
  • the second solution has the second target substance generated by the reaction.
  • Step S22) Extracting the second target: after cooling the second solution to room temperature, pour it into ice water, add aqueous sodium bicarbonate (1M), and neutralize the acidic solution in the second solution by sodium bicarbonate . Then, the extraction was repeated three times using dichloromethane, and the extract obtained by the three extractions was washed three times with water, followed by drying using anhydrous sodium sulfate. The dried extract was filtered and concentrated to obtain the second target.
  • Step S23) Purifying the second target substance: using petroleum ether and dichloromethane (volume ratio of 4:1) as the eluent, the organic matter is separated and purified by a 200-300 mesh silica gel chromatography column to obtain about 4.31g of The first compound in 92% yield.
  • Step S30) Synthesis of the first target compound The first compound (2.35g, 5mmol), the second compound (2.88g, 5.5mmol), tetrahydrofuran (10mL) and sodium carbonate aqueous solution (5mL, 1.6M) were placed in a In the reaction vessel, nitrogen gas was introduced for deoxygenation treatment. Then, tetrakis(triphenylphosphonium)palladium (0.24 g, 0.2 mmol) was added, and the reaction was carried out at a temperature of 50°C-100°C, preferably 80°C, for 24 hours to obtain a first solution.
  • the first solution has a first target compound synthesized by reaction.
  • the molecular structure of the second compound contains at least one aryl group or heteroaryl group.
  • Step S50 purifying the first target substance: using petroleum ether and dichloromethane (volume ratio of 5:1) as the eluent, the organic matter is separated and purified by a 200-300 mesh silica gel chromatography column to obtain about 3.78g of Hole transport material in 91% yield.
  • the second compound is 4-[bis-(4-phenyl)-amino]-phenylboronic acid ester.
  • the preparation process of the hole transport material is shown in formula 9
  • the structures of L in the molecular structural formula of the hole transport material are respectively:
  • the structure of L can also be one of the following structures:
  • the introduced aromatic amine can effectively improve the hole injection and transport performance of the organic material, thereby improving the balance of electrons and holes in the electroluminescent device, and achieving a lower voltage and higher efficiency.
  • the introduction of an alkyl, aryl or heteroaryl structure at the 4-position of fluorene can adjust the evaporation temperature, melting or sublimation characteristics, mobility, etc. of the material, which is beneficial to the stability of mass production evaporation and improves the performance of the device.
  • This example is the application of the hole transport material prepared in the above examples 1-3, which is applied in an electroluminescent device.
  • an electroluminescence device is provided in this embodiment.
  • the electroluminescence device includes a substrate layer 1 , a first electrode 2 , a hole injection layer 3 , a hole transport layer 4 , and an electron A blocking layer 5 , a light emitting layer 6 , an electron transport layer 7 , an electron injection layer 8 and a second electrode 9 .
  • the substrate layer 1 is a glass substrate layer for protecting the overall structure of the electroluminescent device.
  • the first electrode 2 is disposed on the substrate layer 1, and its material is indium tin oxide (ITO).
  • the first electrode 2 is used to transmit current and voltage and provide holes.
  • the hole injection layer 3 is disposed on a surface of the first electrode 2 away from the substrate layer 1, and its material is HATCN (Hexanitrilehexaazatriphenylene), and its thickness is 10 nm.
  • the hole injection layer 3 is used for injecting holes inside the hole injection layer 3 into the light emitting layer 6 .
  • the hole transport layer 4 is disposed on a surface of the hole injection layer 3 away from the first electrode 2 , and its material is the hole transport material, and its thickness is 40 nm.
  • the electron blocking layer 5 is disposed on a surface of the hole transport layer 4 away from the hole injection layer 3, and its material is 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA) with a thickness of 20 nm, the electron blocking layer 5 is used to block the electrons in the light-emitting layer 6 from entering the hole transport layer 4.
  • TCTA 4,4',4"-tris(carbazol-9-yl)triphenylamine
  • the light-emitting layer 6 is provided on the electron blocking layer 5 away from the holes
  • its material is tris (2-phenylpyridine) iridium, and its thickness is 30nm
  • the holes provided by the first electrode 2 and the electrons provided by the second electrode 9 are in the current and Under the action of voltage, they are gathered in the light-emitting layer 6 and combined, so as to convert electrical energy into light energy and realize electroluminescence.
  • the electron transport layer 7 is arranged on a part of the light-emitting layer 6 away from the electron blocking layer 5 On the surface, its material is 1,3,5-tris(3-(3-pyridyl)phenyl)benzene (TM3PyPB), and its thickness is 10 nm, and the electron transport layer 7 is used for the electron injection layer 8 The electrons in it are transported into the light-emitting layer 6.
  • the electron injection layer 8 is provided on a surface of the electron transport layer 7 away from the light-emitting layer 6, and its material is B-Phen, and its thickness is 40 nm.
  • the second electrode 9 is disposed on a surface of the electron injection layer 8 away from the electron transport layer 7 , and is made of lithium fluoride and aluminum. The second electrode 9 is used to transmit current and voltage and provide electrons.
  • the electroluminescence devices made of the hole transport material prepared in Examples 1-3 were tested for performance.
  • Table 1 shows the performance data of the electroluminescent devices made from the hole transport materials in Examples 1-3, respectively.
  • the device 1 is made of the hole transport material prepared in Example 1
  • the device 2 is made of the hole transport material prepared in Example 2
  • the device 3 is made of the hole transport material prepared in Example 3.
  • This test mainly detected the highest occupied molecular orbital (LUMO), the highest occupied molecular orbital (HOMO), the lowest triplet energy level (T1), the voltage, the highest current efficiency and the maximum external quantum efficiency.
  • the hole transport material of the present invention has excellent luminescence properties
  • the hole transport layer made of it has better hole injection and transport properties, and can achieve higher external quantum with lower voltage. efficiency, so as to achieve higher luminous efficiency and better stability.
  • the hole transport material can also be used to prepare a hole injection layer.
  • R can also be:
  • the molecular structural formula of the hole transport material may also be one of the following structural formulas:

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Abstract

一种空穴传输材料及其制备方法、电致发光器件。所述空穴传输材料的分子结构的主链中具有螺蒽芴结构，其分子结构的支链结构中具有芳基或杂芳基结构。所提供的空穴传输材料能够有效提高有机材料的空穴注入和传输性能，从而改善电致发光器件的电子和空穴平衡，达到较低的电压和较高的效率。

Description

空穴传输材料及其制备方法、电致发光器件 技术领域
本发明涉及一种显示技术领域，特别是一种空穴传输材料及其制备方法、电致发光器件。
背景技术
有机电子器件是指由阳极、阴极及夹在阳极和阴极之间的有机层构成的器件，包括有机发光二极管、有机太阳能电池、有机半导体、有机晶体等。其工作原理为在电极上施加外加电压，将空穴和电子注入有机层中形成激子，从而辐射发光(有机发光二极管)；或外部光源被有机材料吸收形成激子，而激子分离成空穴、电子被传递至电极而储存(有机太阳能电池)。
有机电子器件的有机层都是一层或多层有机材料，分别为空穴注入或传输材料，电子注入或传输材料，或发光材料等。其中，这些不同的有机材料在不同有机电子器件中都基于相似的原理操作：
有机发光二极管是将电能转化为光能的现象，其结构通常为阳极、阴极及置于其之间的多层有机材料层。有机材料层根据功能分为空穴注入材料，空穴传输材料、电子注入材料、电子传输材料和发光材料。此外，发光材料根据发光颜色又分为蓝色、天蓝色、绿色、黄色、红色和深红色等发光材料。
有机发光二极管的评价指标主要为电压、效率和寿命，如何开发低电压、高效率和长寿命的电致发光器件一直是研发界和商业界追求的目标，这需要高迁移率的电子/空穴注入和传输材料，高效率的发光材料以及器件中电子和空穴的有效平衡。另外，基于有机材料的可量产性，也必须考虑材料的蒸镀类型(升华型或熔融型)、分解温度、玻璃化转变温度和放气现象等。特别是量产中需要蒸镀较厚的空穴传输材料，这种材料中的升华型材料会严重影响量产膜厚的均匀性，所以开发熔融型的空穴传输材料也成为一个重要方向。
技术问题
本发明的目的是提供一种空穴传输材料及其制备方法、显示器件，以解决现有技术中在制备显示器件时，蒸镀的空穴传输材料不稳定、不利于量产等问题。
技术解决方案
为实现上述目的，本发明提供一种空穴传输材料，所述空穴传输材料的分子结构的主链中具有螺蒽芴结构，其分子结构式如下所示：
Figure PCTCN2020138351-appb-000001
其中，Ar 1、Ar 2、Ar 3和Ar 4中包含至少一个芳基或杂芳基；R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种；R 1-R 6分别为氢、氘、C 1-C 60的烷基、C 1-C 60芳基或C 1-C 60杂芳基中的至少一种；a、b、c和d为小于5的整数。
进一步地，所述Ar 1、Ar 2、Ar 3和Ar 4的分子结构为以下结构中的一种：
Figure PCTCN2020138351-appb-000002
其中，所述R 7-R 10和所述L为C 1-C 60的芳基或C 1-C 60杂芳基。
进一步地，所述L为下述基团结构中的一种：
Figure PCTCN2020138351-appb-000003
Figure PCTCN2020138351-appb-000004
进一步地，当a、b、c和d为0时，所述R 3-R 6分别为氢或氘中的一种；当a、b、c和d为1-4时，所述R 3-R 6分别为C 1-C 60的烷基、C 1-C 60芳基或C 1-C 60杂芳基。
进一步地，当a、b、c和d为0时，所述空穴传输材料的分子结构式为：
Figure PCTCN2020138351-appb-000005
进一步地，所述R为以下基团结构中的一种：
Figure PCTCN2020138351-appb-000006
本发明中还提供了一种空穴传输材料的制备方法，所述制备方法中包括以下步骤：
制备第一化合物：所述第一化合物的分子结构中包含以下结构：
Figure PCTCN2020138351-appb-000007
其中，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种；X为卤族元素中的一种。
合成第一目标物：将第一化合物和第二化合物置于反应容器中进行脱氧处理。加入催化剂至所述反应容器中，并在温度50℃-150℃的条件下充分反应得到第一溶液。所述第二化合物的分子结构中包含至少一个芳基或杂芳基。
纯化处理第一目标物：使用淋洗液，通过硅胶柱层析方法纯化所述第一溶液，得到所述空穴传输材料。
进一步地，所述制备第一化合物步骤中还包括以下步骤：
制备第三化合物：所述第三化合物的分子结构中包含下述结构：
Figure PCTCN2020138351-appb-000008
合成第二目标物：将所述第三化合物、浓盐酸和冰醋酸置于反应容器中，在50-100℃的温度下充分反应后加入碳酸氢钠，得到第二溶液，所示第二溶液中含有所述第二目标物。
萃取第二目标物：在所述第二溶液中加入二氯甲烷进行萃取，得到所述第二目标物。
纯化处理第二目标物：使用淋洗液，通过硅胶柱层析方法纯化所述第二目标物，得到所述第一化合物。
进一步地，所述制备第三化合物步骤中包括以下步骤：
将第四化合物溶解在四氢呋喃中，并加入丁基锂，反应后得到反应液。将第五化合物溶解在四氢呋喃中，并滴加至所述反应液中，充分反应后得到第三溶液。去除第三溶液中的液体，得到所述第三化合物。
其中，所述第四化合物的分子结构中包含以下结构：
Figure PCTCN2020138351-appb-000009
所述第四化合物的分子结构中的Y为卤族元素。所述第五化合物的分子结构式中具有蒽结构。
本发明中还提供一种电致发光器件，所述电致发光器件中包括衬底层、第一电极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层以及第二电极。所述第一电极设于所述衬底层上。所述空穴注入层设于所述第一电极上。所述空穴传输层设于所述空穴注入层上。所述发光层设于所述空穴传输层上。所述电子传输层设于所述发光层上。所述电子注入层设于所述电子传输层上。所述第二电极设于所述电子注入层上。
其中，所述空穴注入层和/或所述空穴传输层中具有如上所述的空穴传输材料。
有益效果
本发明的优点是：本发明的一种空穴传输材料，其分子结构中的芳胺能够有效提高有机材料的空穴注入和传输性能，从而改善电致发光器件的电子和空穴平衡，达到较低的电压和较高的效率。而在芴的4位引入烷基、芳基或杂芳基结构能够调节材料的蒸镀温度，熔融或升华特性，迁移率等，从而有利于量产蒸镀的稳定性和提高器件的性能。
附图说明
图1为本发明应用实施例中电致发光器件的层状结构示意图。
图中部件表示如下：
衬底层1；第一电极2；
空穴注入层3；空穴传输层4；
电子阻挡层5；发光层6；
电子传输层7；电子注入层8；
第二电极9。
本发明的实施方式
以下为本发明的具体实施例，证明本发明可以实施，所述发明实施例可以向本领域中的技术人员完整介绍本发明，使其技术内容更加清楚和便于理解。本发明可以通过许多不同形式的发明实施例来得以体现，本发明的保护范围并非仅限 于文中提到的实施例。
实施例1
本发明实施例中提供了一种空穴传输材料，所述空穴传输材料的分子结构式中的主链为螺蒽芴结构，其分子结构式为：
Figure PCTCN2020138351-appb-000010
其中，Ar 1、Ar 2、Ar 3和Ar 4中包含至少一个芳基或杂芳基；R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种；R 1-R 6分别为氢、氘、C 1-C 60的烷基、C 1-C 60芳基或C 1-C 60杂芳基中的至少一种；a、b、c和d为小于5的整数。
具体的，在本发明实施例中，所述Ar1为的分子结构为：
Figure PCTCN2020138351-appb-000011
并且R 7和R 8为芳基结构或杂芳基结构。
所述R为的结构式为：
Figure PCTCN2020138351-appb-000012
所述a-d均为0，且R 1-R 6均为氢键。
具体的，所述空穴传输材料的分子结构式为：
Figure PCTCN2020138351-appb-000013
本发明实施例中还提供了上述空穴传输材料的制备方法，其包括以下制备步骤：
步骤S10)制备第三化合物：所述第三化合物的分子结构式中包含以下结构：
Figure PCTCN2020138351-appb-000014
其中，此分子结构式中的X为卤族元素，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种。
具体的，制备第三化合物步骤中包括：
将第四化合物(11mmol,3.43g)和四氢呋喃(20mL)加入至一反应容器中，并将所述反应容器置于氩气环境下，搅拌溶解。将反应容器置于温度为-60℃至-90℃，优选为-78℃的环境下，缓慢滴入丁基锂(7.5mL，1.6M)，并保温反应1小时，得到反应液。其中，所述第四化合物的分子结构中包含以下结构：
Figure PCTCN2020138351-appb-000015
此分子结构式中的X和Y均为卤族元素，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种。
将第五化合物(10mmol，2.22g)溶解在四氢呋喃(20mL)中，并也在温度为-60℃至-90℃，优选为-78℃的环境下缓慢滴入所述反应液中。滴加结束后，将所述反应液升温至室温，并反应12小时。反应结束后，加入适量氯化铵淬灭反应，得到所述第三溶液。通过旋转去除所述第三溶液中的液体，得到所述第三化合物。其中，所述第五化合物的分子结构式中具有蒽结构。
具体的，所述第四化合物为1-溴-3’-氯-4-苯基联苯，所述第五化合物为9，9-二甲基蒽酮。所述第三化合物的制备流程式如式1所示：
Figure PCTCN2020138351-appb-000016
步骤S20)制备第一化合物：所述第一化合物的分子结构式中包含以下结构：
Figure PCTCN2020138351-appb-000017
其中，此分子结构式中的X为卤族元素，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种。
具体的，制备第一化合物步骤中包括以下步骤：
步骤S21)合成第二目标物：将步骤S10中所得到的第三化合物置于一反应容器中，并加入浓盐酸(5mL)和冰醋酸(15mL)，并在温度为50-100℃，优选为80℃的环境下反应24小时，得到第二溶液。所述第二溶液中具有反应生成的第二目标物。
步骤S22)萃取第二目标物：将所述第二溶液冷却至室温后，将其倒入冰水中，并加入碳酸氢钠水溶液(1M)，通过碳酸氢钠中和第二溶液中的酸性溶液。然后使用二氯甲烷反复萃取三次，并将三次萃取所得的萃取物水洗三次，随后使用无水硫酸钠进行干燥。将干燥后的萃取物进行过滤及浓缩，得到所述第二目标物。
步骤S23)纯化处理第二目标物：使用石油醚和二氯甲烷(体积比为4:1)作为淋洗剂，通过200-300目的硅胶层析柱对有机物进行分离纯化，得到约4.31g的第一化合物，产率为92％。
具体的，所述第一化合物的制备流程式如式2所示：
Figure PCTCN2020138351-appb-000018
步骤S30)合成第一目标物：将所述第一化合物(2.35g，5mmol)、第二化合物(1.61g，5mmol)、t-BuONa(8mmol，0.76g)以及甲苯(30mL)置于一反应容器中，并通入氮气进行脱氧处理。然后加入三(二亚苄基丙酮)二钯(0.09mmol,81mg)和四氟硼酸三叔丁基膦(0.92mmol,0.24g)，在温度为100℃-150℃，优选为110℃的环境下充分反应，得到第一溶液。所述第一溶液中具有反应合成的第一目标物。其中，所述第二化合物的分子结构中包含至少一个芳基或杂芳基。
步骤S40)纯化处理第一目标物：将所述第一溶液降温至室温后，将第一溶液浓缩，得到上所述第一目标物。然后使用200-300目的硅胶柱层析对第一目标物中的有机物进行分离纯化，得到约3.21g的空穴传输材料，产率为85％。
具体的，所述第二化合物为二-4-苯基-苯胺。所述空穴传输材料的制备流程式如式3所示
Figure PCTCN2020138351-appb-000019
本发明实施例中所提供的空穴传输材料，其所引入的芳胺能够有效提高有机材料的空穴注入和传输性能，从而改善电致发光器件的电子和空穴平衡，达到较低的电压和较高的效率。而在芴的4位引入烷基、芳基或杂芳基结构能够调节材 料的蒸镀温度，熔融或升华特性，迁移率等，从而有利于量产蒸镀的稳定性和提高器件的性能。
实施例2
本发明实施例中提供了一种空穴传输材料，所述空穴传输材料的分子结构式中的主链为螺蒽芴结构，其分子结构式为：
Figure PCTCN2020138351-appb-000020
其中，Ar 1、Ar 2、Ar 3和Ar 4中包含至少一个芳基或杂芳基；R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种；R 1-R 6分别为氢、氘、C 1-C 60的烷基、C 1-C 60芳基或C 1-C 60杂芳基中的至少一种；a、b、c和d为小于5的整数。
具体的，在本发明实施例中，所述Ar1为的分子结构为：
Figure PCTCN2020138351-appb-000021
并且R 7和R 8为芳基结构或杂芳基结构。
所述R为的结构式为：
Figure PCTCN2020138351-appb-000022
所述a-d均为0，且R 1-R 6均为氢键。
具体的，所述空穴传输材料的分子结构式为：
Figure PCTCN2020138351-appb-000023
本发明实施例中还提供了上述空穴传输材料的制备方法，其包括以下制备步骤：
步骤S10)制备第三化合物：所述第三化合物的分子结构式中包含以下结构：
Figure PCTCN2020138351-appb-000024
其中，此分子结构式中的X为卤族元素，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种。
具体的，制备第三化合物步骤中包括：
将第四化合物(11mmol,3.55g)和四氢呋喃(20mL)加入至一反应容器中，并将所述反应容器置于氩气环境下，搅拌溶解。将反应容器置于温度为-60℃至-90℃，优选为-78℃的环境下，缓慢滴入丁基锂(7.5mL，1.6M)，并保温反应1小时，得到反应液。其中，所述第四化合物的分子结构中包含以下结构：
Figure PCTCN2020138351-appb-000025
此分子结构式中的X和Y均为卤族元素，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种。
将第五化合物(10mmol，2.22g)溶解在四氢呋喃(20mL)中，并也在温度为-60℃至-90℃，优选为-78℃的环境下缓慢滴入所述反应液中。滴加结束后， 将所述反应液升温至室温，并反应12小时。反应结束后，加入适量氯化铵淬灭反应，得到所述第三溶液。通过旋转去除所述第三溶液中的液体，得到所述第三化合物。其中，所述第五化合物的分子结构式中具有蒽结构。
具体的，所述第四化合物为1-溴-3’-氯-4-叔丁基联苯，所述第五化合物为9，9-二甲基蒽酮。所述第三化合物的制备流程式如式4所示：
Figure PCTCN2020138351-appb-000026
步骤S20)制备第一化合物：所述第一化合物的分子结构式中包含以下结构：
Figure PCTCN2020138351-appb-000027
其中，此分子结构式中的X为卤族元素，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种。
具体的，制备第一化合物步骤中包括以下步骤：
步骤S21)合成第二目标物：将步骤S10中所得到的第三化合物置于一反应容器中，并加入浓盐酸(5mL)和冰醋酸(15mL)，并在温度为50-100℃，优选为80℃的环境下反应24小时，得到第二溶液。所述第二溶液中具有反应生成的第二目标物。
步骤S22)萃取第二目标物：将所述第二溶液冷却至室温后，将其倒入冰水中，并加入碳酸氢钠水溶液(1M)，通过碳酸氢钠中和第二溶液中的酸性溶液。然后使用二氯甲烷反复萃取三次，并将三次萃取所得的萃取物水洗三次，随后使用无水硫酸钠进行干燥。将干燥后的萃取物进行过滤及浓缩，得到所述第二目标物。
步骤S23)纯化处理第二目标物：使用石油醚和二氯甲烷(体积比为5:1)作为淋洗剂，通过200-300目的硅胶层析柱对有机物进行分离纯化，得到约3.95g的第一化合物，产率为88％。
具体的，所述第一化合物的制备流程式如式5所示：
Figure PCTCN2020138351-appb-000028
步骤S30)合成第一目标物：将所述第一化合物(2.25g，5mmol)、第二化合物(1.61g，5mmol)、t-BuONa(8mmol，0.76g)以及甲苯(30mL)置于一反应容器中，并通入氮气进行脱氧处理。然后加入三(二亚苄基丙酮)二钯(0.09mmol,81mg)和四氟硼酸三叔丁基膦(0.92mmol,0.24g)，在温度为100℃-130℃，优选为110℃的环境下充分反应，得到第一溶液。所述第一溶液中具有反应合成的第一目标物。其中，所述第二化合物的分子结构中包含至少一个芳基或杂芳基。
步骤S40)纯化处理第一目标物：将所述第一溶液降温至室温后，将第一溶液浓缩，得到上所述第一目标物。然后使用200-300目的硅胶柱层析对第一目标物中的有机物进行分离纯化，得到约3.16g的空穴传输材料，产率为86％。
具体的，所述第二化合物为二-4-苯基-苯胺。所述空穴传输材料的制备流程式如式6所示
Figure PCTCN2020138351-appb-000029
本发明实施例中所提供的空穴传输材料，其所引入的芳胺能够有效提高有机材料的空穴注入和传输性能，从而改善电致发光器件的电子和空穴平衡，达到较低的电压和较高的效率。而在芴的4位引入烷基、芳基或杂芳基结构能够调节材料的蒸镀温度，熔融或升华特性，迁移率等，从而有利于量产蒸镀的稳定性和提高器件的性能。
实施例3
本发明实施例中提供了一种空穴传输材料，所述空穴传输材料的分子结构式中的主链为螺蒽芴结构，其分子结构式为：
Figure PCTCN2020138351-appb-000030
其中，Ar 1、Ar 2、Ar 3和Ar 4中包含至少一个芳基或杂芳基；R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种；R 1-R 6分别为氢、氘、C 1-C 60的烷基、C 1-C 60芳基或C 1-C 60杂芳基中的至少一种；a、b、c和d为小于5的整数。
具体的，在本发明实施例中，所述Ar1的分子结构为：
Figure PCTCN2020138351-appb-000031
并且R 9和R 10为芳基结构或杂芳基结构，L的结构为：
Figure PCTCN2020138351-appb-000032
所述R的结构为：
Figure PCTCN2020138351-appb-000033
所述a-d均为0，且R 1-R 6均为氢键。
具体的，所述空穴传输材料的分子结构式为：
Figure PCTCN2020138351-appb-000034
本发明实施例中还提供了上述空穴传输材料的制备方法，其包括以下制备步骤：
步骤S10)制备第三化合物：所述第三化合物的分子结构式中包含以下结构：
Figure PCTCN2020138351-appb-000035
其中，此分子结构式中的X为卤族元素，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种。
具体的，制备第三化合物步骤中包括：
将第四化合物(11mmol,3.43g)和四氢呋喃(20mL)加入至一反应容器中，并将所述反应容器置于氩气环境下，搅拌溶解。将反应容器置于温度为-60℃至-90℃，优选为-78℃的环境下，缓慢滴入丁基锂(7.5mL，1.6M)，并保温反应1小时，得到反应液。其中，所述第四化合物的分子结构中包含以下结构：
Figure PCTCN2020138351-appb-000036
此分子结构式中的X和Y均为卤族元素，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种。
将第五化合物(10mmol，2.22g)溶解在四氢呋喃(20mL)中，并也在温度为-60℃至-90℃，优选为-78℃的环境下缓慢滴入所述反应液中。滴加结束后，将所述反应液升温至室温，并反应12小时。反应结束后，加入适量氯化铵淬灭 反应，得到所述第三溶液。通过旋转去除所述第三溶液中的液体，得到所述第三化合物。其中，所述第五化合物的分子结构式中具有蒽结构。
具体的，所述第四化合物为1-溴-3’-氯-4-苯基联苯，所述第五化合物为9，9-二甲基蒽酮。所述第三化合物的制备流程式如式7所示：
Figure PCTCN2020138351-appb-000037
步骤S20)制备第一化合物：所述第一化合物的分子结构式中包含以下结构：
Figure PCTCN2020138351-appb-000038
其中，此分子结构式中的X为卤族元素，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种。
具体的，制备第一化合物步骤中包括以下步骤：
步骤S21)合成第二目标物：将步骤S10中所得到的第三化合物置于一反应容器中，并加入浓盐酸(5mL)和冰醋酸(15mL)，并在温度为50-100℃，优选为80℃的环境下反应24小时，得到第二溶液。所述第二溶液中具有反应生成的第二目标物。
步骤S22)萃取第二目标物：将所述第二溶液冷却至室温后，将其倒入冰水中，并加入碳酸氢钠水溶液(1M)，通过碳酸氢钠中和第二溶液中的酸性溶液。然后使用二氯甲烷反复萃取三次，并将三次萃取所得的萃取物水洗三次，随后使用无水硫酸钠进行干燥。将干燥后的萃取物进行过滤及浓缩，得到所述第二目标物。
步骤S23)纯化处理第二目标物：使用石油醚和二氯甲烷(体积比为4:1)作为淋洗剂，通过200-300目的硅胶层析柱对有机物进行分离纯化，得到约4.31g的第一化合物，产率为92％。
具体的，所述第一化合物的制备流程式如式8所示：
Figure PCTCN2020138351-appb-000039
步骤S30)合成第一目标物：将所述第一化合物(2.35g，5mmol)、第二化合物(2.88g，5.5mmol)、四氢呋喃(10mL)以及碳酸钠水溶液(5mL，1.6M)置于一反应容器中，并通入氮气进行脱氧处理。然后加入四(三苯基磷)合钯(0.24g，0.2mmol)，在温度为50℃-100℃，优选为80℃的环境下反应24小时，得到第一溶液。所述第一溶液中具有反应合成的第一目标物。其中，所述第二化合物的分子结构中包含至少一个芳基或杂芳基。
步骤S40)萃取第一目标物：将所述第一溶液降温至室温后，然后使用二氯甲烷反复萃取三次，并将三次萃取所得的萃取物水洗三次，随后使用无水硫酸钠进行干燥。将干燥后的萃取物进行过滤、旋干，得到所述第一目标物。
步骤S50)纯化处理第一目标物：使用石油醚和二氯甲烷(体积比为5:1)作为淋洗剂，通过200-300目的硅胶层析柱对有机物进行分离纯化，得到约3.78g的空穴传输材料，产率为91％。
具体的，所述第二化合物为4-[二-(4-苯基)-氨基]-苯硼酸酯。所述空穴传输材料的制备流程式如式9所示
Figure PCTCN2020138351-appb-000040
在本发明实施例中，所述空穴传输材料的分子结构式中的L的结构分别为：
Figure PCTCN2020138351-appb-000041
但在发明的其他实施例中，L的结构还可以为以下结构中的一种：
Figure PCTCN2020138351-appb-000042
Figure PCTCN2020138351-appb-000043
本发明实施例中所提供的空穴传输材料，其所引入的芳胺能够有效提高有机材料的空穴注入和传输性能，从而改善电致发光器件的电子和空穴平衡，达到较低的电压和较高的效率。而在芴的4位引入烷基、芳基或杂芳基结构能够调节材料的蒸镀温度，熔融或升华特性，迁移率等，从而有利于量产蒸镀的稳定性和提高器件的性能。
应用实施例
本实施例是上述实施例1-3所制得的空穴传输材料的应用，其应用在电致发光器件中。
如图1所示，本实施例中提供一种电致发光器件，所述电致发光器件包括一衬底层1、一第一电极2、一空穴注入层3、一空穴传输层4、一电子阻挡层5、一发光层6、一电子传输层7、一电子注入层8以及一第二电极9。
所述衬底层1为玻璃衬底层，用于保护所述电致发光器件的整体结构。所述第一电极2设于所述衬底层1上，其材料为氧化铟锡(ITO)。所述第一电极2用于传输电流电压，提供空穴。所述空穴注入层3设于所述第一电极2远离所述衬底层1的一表面上，其材料为HATCN(Hexanitrilehexaazatriphenylene，六腈六氮杂苯并菲)，其厚度为10nm，所述空穴注入层3用于将其内部的空穴注入至所述发光层6内。所述空穴传输层4设于所述空穴注入层3远离所述第一电极2的一表面上，其材料为所述空穴传输材料，其厚度为40nm，所述空穴传输层4用于将所述空穴注入层3内的空穴传输至所述发光层6内。所述电子阻挡层5设于所述空穴传输层4远离所述空穴注入层3的一表面上，其材料为4,4',4”-三(咔唑-9-基)三苯胺(TCTA)，其厚度为20nm，所述电子阻挡层5用于阻挡发光层6中的电子进入空穴传输层4中。所述发光层6设于所述电子阻挡层5远离所述空穴传输层4的一表面上，其材料为三(2-苯基吡啶)合铱，其厚度为30nm，所述第一电极2提供的空穴和所述第二电极9提供的电子在电流和电压的作用下汇聚在所述发光层6内并结合，从而将电能转换为光能，实现电致发光。所述电子传输层7设于所述发光层6远离所述电子阻挡层5的一表面上，其材料为 1,3,5-三(3-(3-吡啶基)苯基)苯(TM3PyPB)，其厚度为10nm，所述电子传输层7用于将所述电子注入层8中的电子传输至所述发光层6内。所述电子注入层8设于所述电子传输层7远离所述发光层6的一表面上，其材料为B-Phen，其厚度为40nm。所述第二电极9设于所述电子注入层8远离所述电子传输层7的一表面上，其材料为氟化锂和铝，所述第二电极9用于传输电流电压，提供电子。
为了更好的说明本发明中的空穴传输材料的性能，对由实施例1-3中所制备的空穴传输材料制成的电致发光器件进行了性能测试。由实施例1-3中的空穴传输材料分别所制成的电致发光器件的性能数据如表1所示。其中，器件1由实施例1中制备的空穴传输材料制成，器件2由实施例2中制备的空穴传输材料制成，器件3由实施例3中制备的空穴传输材料制成。本次测试主要检测了最高占据分子轨道(LUMO)、最高占据分子轨道(HOMO)、最低三重态能级(T1)、电压、最高电流效率以及最大外量子效率。
Figure PCTCN2020138351-appb-000044
表1
由表1可知，本发明的空穴传输材料具有优良的发光性能，由其制成的空穴传输层具有更好的空穴注入和传输性能，能够用较低的电压达到较高的外量子效率，从而达到使发光效率更高，稳定性更好。
在本发明的其他应用实施例中，所述空穴传输材料还可以用于制备空穴注入层。
在本发明实施例1-实施例3中，所述空穴传输材料的分子结构式中的R的结构分别为：
Figure PCTCN2020138351-appb-000045
但在发明的其他实施例中，R的结构还可以为：
Figure PCTCN2020138351-appb-000046
在本发明的其他实施例中，所述空穴传输材料的分子结构式还可以为以下结构式中的一种：
Figure PCTCN2020138351-appb-000047
Figure PCTCN2020138351-appb-000048
Figure PCTCN2020138351-appb-000049
Figure PCTCN2020138351-appb-000050
Figure PCTCN2020138351-appb-000051
Figure PCTCN2020138351-appb-000052
其制备方法与本发明中的实施例相似，因此不在此做过多赘述。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其它实施例，都属于本申请保护的范围。
虽然在本文中参照了特定的实施方式来描述本发明，但是应该理解的是，这些实施例仅仅是本发明的原理和应用的示例。因此应该理解的是，可以对示例性 的实施例进行许多修改，并且可以设计出其他的布置，只要不偏离所附权利要求所限定的本发明的精神和范围。应该理解的是，可以通过不同于原始权利要求所描述的方式来结合不同的从属权利要求和本文中所述的特征。还可以理解的是，结合单独实施例所描述的特征可以使用在其他所述实施例中。

Claims (10)

  1. 一种空穴传输材料，其中，所述空穴传输材料的分子结构的主链中具有螺蒽芴结构，其分子结构式如下所示：
    Figure PCTCN2020138351-appb-100001
    其中，Ar 1、Ar 2、Ar 3和Ar 4中包含至少一个芳基或杂芳基；
    R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种；
    R 1-R 6分别为氢、氘、C 1-C 60的烷基、C 1-C 60芳基或C 1-C 60杂芳基中的至少一种；
    a、b、c和d为小于5的整数。
  2. 如权利要求1所述的空穴传输材料，其中，所述Ar 1、Ar 2、Ar 3和Ar 4的分子结构为以下结构中的一种：
    Figure PCTCN2020138351-appb-100002
    其中，所述R 7-R 10和所述L为C 1-C 60的芳基或C 1-C 60杂芳基。
  3. 如权利要求2所述的空穴传输材料，其中，所述L为下述基团结构中的一种：
    Figure PCTCN2020138351-appb-100003
    Figure PCTCN2020138351-appb-100004
  4. 如权利要求1所述的空穴传输材料，其中，当a、b、c和d为0时，所述R 3-R 6分别为氢或氘中的一种；当a、b、c和d为1-4时，所述R 3-R 6分别为C 1-C 60的烷基、C 1-C 60芳基或C 1-C 60杂芳基。
  5. 如权利要求4所述的空穴传输材料，其中，当a、b、c和d为0时，所述空穴传输材料的分子结构式为：
    Figure PCTCN2020138351-appb-100005
  6. 如权利要求1所述的空穴传输材料，其中，所述R为以下基团结构中的一种：
    Figure PCTCN2020138351-appb-100006
  7. 一种空穴传输材料的制备方法，其中，包括以下步骤：
    制备第一化合物：所述第一化合物的分子结构中包含以下结构：
    Figure PCTCN2020138351-appb-100007
    其中，R为C 1-C 60的烷基、C 1-C 60的芳基或C 1-C 60的杂芳基中的至少一种；X为卤族元素中的一种；
    合成第一目标物：将第一化合物和第二化合物置于反应容器中进行脱氧处理；加入催化剂至所述反应容器中，并在温度50℃-150℃的条件下充分反应得到第一溶液；所述第二化合物的分子结构中包含至少一个芳基或杂芳基；
    纯化处理第一目标物：使用淋洗液，通过硅胶柱层析方法纯化所述第一溶液，得到所述空穴传输材料。
  8. 如权利要求7所述的空穴传输材料的制备方法，其中，所述制备第一化合物步骤中还包括以下步骤：
    制备第三化合物：所述第三化合物的分子结构中包含下述结构：
    Figure PCTCN2020138351-appb-100008
    合成第二目标物：将所述第三化合物、浓盐酸和冰醋酸置于反应容器中，在50-100℃的温度下充分反应后加入碳酸氢钠，得到第二溶液，所示第二溶液中含有所述第二目标物；
    萃取第二目标物：在所述第二溶液中加入二氯甲烷进行萃取，得到所述第二目标物；
    纯化处理第二目标物：使用淋洗液，通过硅胶柱层析方法纯化所述第二目标物，得到所述第一化合物；
  9. 如权利要求8所述的空穴传输材料的制备方法，其中，所述制备第三化合 物步骤中包括以下步骤：
    将第四化合物溶解在四氢呋喃中，并加入丁基锂，反应后得到反应液；将第五化合物溶解在四氢呋喃中，并滴加至所述反应液中，充分反应后得到第三溶液；去除第三溶液中的液体，得到所述第三化合物；
    其中，所述第四化合物的分子结构中包含以下结构：
    Figure PCTCN2020138351-appb-100009
    所述Y为卤族元素；
    所述第五化合物的分子结构式中具有蒽结构。
  10. 一种电致发光器件，其中，包括：
    衬底层；
    第一电极，设于所述衬底层上；
    空穴注入层，设于所述第一电极上；
    空穴传输层，设于所述空穴注入层上；
    发光层，设于所述空穴传输层上；
    电子传输层，设于所述发光层上；
    电子注入层，设于所述电子传输层上；
    第二电极，设于所述电子注入层上；
    其中，所述空穴注入层和/或所述空穴传输层中具有如权利要求1中所述的空穴传输材料。
PCT/CN2020/138351 2020-12-08 2020-12-22 空穴传输材料及其制备方法、电致发光器件 Ceased WO2022120945A1 (zh)

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