Hole transport material, manufacturing method thereof, and electroluminescent device thereof

Abstract

The present invention provides an improved hole transport material, manufacturing method and an electroluminescent device having a central core made of tetramethyldihydrophenazine. A structural formula of the hole transport material is: ##STR00001##
The present invention adjusts the structure of donor units to change a capability of providing electrons thereof, designs a hole transport material of a high mobility and reasonable wires, and the material improves the compounding efficiency.

Claims

1. An electroluminescent device, comprising: a substrate layer, a hole injection layer, a transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a translucent electrode, and an optical coupling output layer that are sequentially stacked on one another; wherein the substrate layer comprises glass and a total reflection underlay layer including an indium tin oxide (ITO) layer, an Ag layer and an ITO layer that are stacked sequentially, and the Ag layer is a reflective surface configured to make an output light emitted from a top of the device; wherein the hole injection layer is configured to inject holes from the ITO layers into an organic light emitting diode (OLED) device, and is made of MoO3; wherein the hole transport layer is configured to transport the holes injected and is capable of adjusting a resonant wavelength of a microcavity by adjusting a thickness of the hole transport layer, and the hole transport layer is made of a hole transport material comprising a central core made of tetramethyldihydrophenazine, wherein a structural formula of the hole transport material is: ##STR00026## wherein each of the R1 group and the R2 group is selected from structural formulas as follows: ##STR00027## ##STR00028## wherein the electron blocking layer is configured to block and hold electrons injected into the light emitting layer in the light emitting layer to prevent the electrons from being transported to the hole transport layer, and to restrict a composite region of excitons in the light emitting layer, and the electron blocking layer is made of (4-[1-[4-[bis(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC); wherein the light emitting layer is configured to combine the holes and the electrons to form excitons, a fluorescent material emits light by the excitons, and the light emitting layer is made of 4,4′-bis(9-carbazole)biphenyl: tris(2-phenylpyridine)iridium (Ill) doped; wherein the hole blocking layer is configured to block and hold holes injected into the light emitting layer in light emitting layer to prevent the holes from being transported to the electron transport layer, and to restrict, and to restrict a composite region of excitons in the light emitting layer, and the hole blocking layer is made of 1,3,5-Tris (3-pyridyl-3-phenyl)benzene (Tm3PyPB); wherein the electron transport layer is configured to transport the electrons injected, is made of 1,3,5-Tris(3-pyridyl-3-phenyl)benzene Tm3PyPB and 8-Hydroxyquinoline aluminum salt (LiQ), and the electron transport layer is configured to transport the electrons to the light emitting layer; wherein the electron injection layer is configured to inject electrons into the OLED device; wherein the translucent electrode is configured to translucent emission and transmission, is capable of adjusting strength of the microcavity, and is made of magnesium/silver translucent electrode; and wherein the coupling output layer is configured to implement coupling extraction to light and enhance light output rate, and the coupling output layer is made of 4,4′,4″-tris[4-(carbazol-9-yl)phenyl]amine (TCTA).

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic structural view of an electroluminescent device of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(2) In a field of organic light emitting diode (OLED) display screens, a hole transport material is configured to transport holes and simultaneously perform a function of adjusting a microcavity, a consumption amount thereof is the greatest in the entire OLED device, and a thickness of the film layers is also the greatest. A mobility of holes thereof is the key factor of efficiency and lifespan of the OLED device. The present invention on the basis of the central core of the tetramethyldihydrophenazine designs and compounds a series of hole transport materials for compounds. Finally, electroluminescent devices based on the targeted hole transport material have very high efficiency. An objective of the present invention is to achieve matching Highest Occupied Molecular Orbital (HOMO)/Lowest Unoccupied Molecular Orbital (LUMO) energy level, compounding of a hole transport material with high mobility and applications thereof in light emitting devices.

(3) To achieve the above inventive objective of the, the present invention provides a hole transport material comprising a central core made of tetramethyldihydrophenazine. A structural formula of the hole transport material is:

(4) ##STR00014##
wherein each of the R.sub.1 and the R.sub.2 groups can be selected from structural formulas as follows:

(5) ##STR00015## ##STR00016##

(6) By the structural formula of the hole transport material acquired by mutual reaction of the raw material of the central core and electron donors, the hole transport material is selected from three compounds as follows:

(7) ##STR00017##

(8) The present invention also provides a method for manufacturing a hole transport material comprising: step 1), step 2), step 3), and step 4).

(9) The step 1) proportionally adds raw materials including a central core raw material and an electron donor, and mixing the raw materials with a solvent as a reaction solution.

(10) The step 2) adds a catalyst of palladium (II) acetate (Pd(OAc).sub.2) and a tri-tert-butylphosphine tetrafluoroborate into the reaction solution, and adding toluene free of water and oxygen under an atmosphere of argon gas in the reaction solution, heating the raw materials, the solvent, the catalyst, and the toluene in the reaction solution for reaction by 20-24 hours, and cooling the reaction solution to a room temperature.

(11) The step 3) pours the reaction solution into ice water, extracting extracts of organic phase three times by dichloromethane to combine the extract of organic phase, and spinning the extracts of organic phase combined to form silicone.

(12) The step 4) implements separation and purification of column chromatography to acquire white powder to acquire a finished product of the hole transport material.

(13) The solvent is made of palladium (II) acetate (Pd(OAc).sub.2) and tri-tert-butylphosphine tetrafluoroborate ((t-Bu).sub.3HPBF.sub.4).

(14) Preferably, the step 2) adds toluene free of water and oxygen under an atmosphere of argon gas in the reaction solution, for reaction at 120° C. by 24 hours, and cools the reaction solution to a room temperature.

(15) Preferably, an input amount of the electron donor is 2.73 g, and a molar amount of the electron donor is 5 mmol. An input amount of the electron donor is 2.0-2.5 g, a molar amount of the electron donor is 12 mmol, an input amount of the palladium (II) acetate is 0.18 g, an molar amount of the palladium (II) acetate is 0.8 mmol, an input amount of the tri-tert-butylphosphine tetrafluoroborate is 0.68 g, and a molar amount of the tri-tert-butylphosphine tetrafluoroborate is 2.4 mmol.

(16) Preferably, the step 4) adds dichloromethane and hexane for implementing separation and purification of column chromatography, a volume ratio of dichloromethane and hexane is 1:5. After separation and purification of column chromatography, white powder is acquired, i.e., the hole transport material.

(17) Three embodiments as follows are introduced for explaining compounding methods and compounding reactions of hole transport materials of three structural formulas.

First Embodiment

(18) A hole transport material 1 is compounded, a compounding path thereof is as follows:

(19) ##STR00018##

(20) Compounding Step:

(21) A raw material 1

(22) ##STR00019##
(2.73 g, 5 mmol), carbazole

(23) ##STR00020##
(2.00 g, 12 mmol), palladium (II) acetate (0.18 g, 0.8 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.68 g, 2.4 mmol) are added into a dual mouth bottle of 250 mL, and then NaOt-Bu (1.16 g, 12 mmol) is added into a glovebox, toluene of 100 mL free of water and oxygen is added into the reaction solution in advance under an atmosphere of argon gas for reaction at 120° C. by 24 hours. The reaction solution above are cooled to a room temperature, and the reaction solution is poured into ice water of 200 mL, extracts of organic phase are extracted three times by dichloromethane to combine the extract of organic phase, and the extracts of organic phase combined are spun to form silicone. Separation and purification of column chromatography (dichloromethane:hexane, v:v, 1:5) is implemented to acquire white powder of 3.3 g, and a yield rate is 92%. After spectrometric analysis, MS (EI) m/z: [M]+ is 720.31.

Second Embodiment

(24) A hole transport material 2 is compounded, a compounding path thereof is as follows:

(25) ##STR00021##
A compounding step:

(26) A raw material 1

(27) ##STR00022##
(2.73 g, 5 mmol), diphenylamine

(28) ##STR00023##
(2.03 g, 12 mmol), palladium (II) acetate (0.18 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.68 g, 2.4 mmol) are added into a dual mouth bottle of 250 mL, and then NaOt-Bu (1.16 g, 12 mmol) is added into a glovebox, toluene of 100 mL free of water and oxygen is added into the reaction solution in advance under an atmosphere of argon gas for reaction at 120° C. by 24 hours. The reaction solution above are cooled to a room temperature, and the reaction solution is poured into ice water of 200 mL, extracts of organic phase are extracted three times by dichloromethane to combine the extract of organic phase, and the extracts of organic phase combined are spun to form silicone. Separation and purification of column chromatography (dichloromethane:hexane, v:v, 1:5) is implemented to acquire white powder of 2.9 g, and a yield rate is 80%. After spectrometric analysis, MS (EI)m/z: [M]+ is 720.31.

Third Embodiment

(29) A hole transport material 3 is compounded, a compounding path there of is as follows:

(30) ##STR00024##

(31) A raw material 1

(32) ##STR00025##
(2.73 g, 5 mmol), N,N-dimethylacridine (2.50 g, 12 mmol), palladium (II) acetate (0.18 g, 0.8 mmol) tri-tert-butylphosphine tetrafluoroborate (0.68 g, 2.4 mmol) are added into a dual mouth bottle of 250 mL, and then NaOt-Bu (1.16 g, 12 mmol) is added into a glovebox, toluene of 100 mL free of water and oxygen is added into the reaction solution in advance under an atmosphere of argon gas for reaction at 120° C. by 24 hours. The reaction solution above are cooled to a room temperature, and the reaction solution is poured into ice water of 200 mL, extracts of organic phase are extracted three times by dichloromethane to combine the extract of organic phase, and the extracts of organic phase combined are spun to form silicone. Separation and purification of column chromatography (dichloromethane:hexane, v:v, 1:5) is implemented to acquire white powder of 3.8 g, and a yield rate is 95%. After spectrometric analysis, MS (EI)m/z: [M]+ is 804.31.

(33) An electrochemical energy level of the target molecule is as the following Chart 1.

(34) TABLE-US-00001 HOMO (eV) LUMO (eV) compound 1 −5.53 −2.53 compound 2 −5.61 −2.53 compound 3 −5.58 −2.54

(35) Performance data of the device is as follows:

(36) TABLE-US-00002 Highest Maximum Hole current external quantum transport efficiency efficiency Device layer (cd/A) (CIEx, CIEy) (%) Device 1 Compound 1 40.3 (0.685, 0.291) 38.3% Device 2 Compound 2 41.7 (0.685, 0.292) 39.6% Device 3 Compound 3 40.8 (0.685, 0.291) 38.7%

(37) By inspecting various physical and chemical indexes of different compounded compounds, a hole transport material with high efficiency is presented, an OLED electroluminescent device with a long lifespan is acquired, which is a display device based on electroluminescent device.

(38) With reference to FIG. 1, the present invention also provides an electroluminescent device comprising a glass and total reflection (ITO/Ag/ITO) underlay layer 1, a hole injection layer 2: a P-dopant and transport layer 3 (hole transport layer), electron blocking layer 4, light emitting layer 5, hole blocking layer 6, an electron transport layer 7, an electron injection layer 8, translucent electrode 9, and an optical coupling output layer 10 that are sequentially stacked on one another.

(39) The substrate layer 1 comprises glass and a total reflection underlay layer including an indium tin oxide (ITO) layer, an Ag layer and an ITO layer that are stacked sequentially. The Ag layer is a reflective surface configured to make an output light emitted from a top of the device.

(40) The hole injection layer 2 is configured to transport holes the ITO layers into an organic light emitting diode (OLED) device, and is made of MoO3.

(41) The hole transport layer 3 is configured to transport the holes injected and is capable of adjusting a resonant wavelength of a microcavity by adjusting a thickness of the hole transport layer, and the hole transport layer is made of the hole transport material.

(42) The electron blocking layer 4 is configured to block and hold electrons injected into the light emitting layer in the light emitting layer to prevent the electrons from being transported to the hole transport layer, and to restrict a composite region of excitons in the light emitting layer, and the electron blocking layer is made of (4-[1-[4-[bis(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC).

(43) The light emitting layer 5 is configured to combine the holes and the electrons to form excitons, a fluorescent material emits light by the excitons, and the light emitting layer is made of 4,4′-bis(9-carbazole)biphenyl: tris(2-phenylpyridine)iridium (III) doped.

(44) The hole blocking layer 6 is configured to block and hold holes injected into the light emitting layer in light emitting layer to prevent the holes from being transported to the electron transport layer, and to restrict, and to restrict a composite region of excitons in the light emitting layer, and the hole blocking layer is made of 1,3,5-Tris(3-pyridyl-3-phenyl)benzene (Tm3PyPB).

(45) The electron transport layer 7 is configured to transport the electrons injected, is made of 1,3,5-Tris(3-pyridyl-3-phenyl)benzene Tm3PyPB and 8-Hydroxyquinoline aluminum salt (LiQ), and the electron transport layer is configured to transport the electrons to the light emitting layer.

(46) The electron injection layer 8 is configured to inject electrons into the OLED device, and is generally made of Yb or LiF.

(47) The translucent cathode layer 9 is configured to translucent emission and transmission, is capable of adjusting strength of the microcavity, and is made of magnesium/silver translucent electrode;

(48) The coupling output layer 10 is configured to implement coupling extraction to light and enhance light output rate, and the coupling output layer is made of 4,4′,4″-tris[4-(carbazol-9-yl)phenyl]amine (TCTA).

(49) The structure of the above electroluminescent device for functions of the microcavity and requirement of enhanced color gamut of light of the device for applications, the hole transport material is disposed on the third layer and improves the efficiency of the device by increasing mobility.

(50) The above is only preferred embodiments of the present invention. It should be noted that a person of ordinary skill in the art can make several improvements and modifications without departing from the principle of the present invention. These improvements and modifications should also be considered to be within the scope of protection of the present invention.

INDUSTRIAL APPLICABILITY

(51) The subject matter of the present invention can be manufactured and used in industries and therefore has industrial applicability.