CN113214254B - Hole-transport-type main body material, preparation method thereof and application thereof in preparation of organic electroluminescent device - Google Patents
Hole-transport-type main body material, preparation method thereof and application thereof in preparation of organic electroluminescent device Download PDFInfo
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- CN113214254B CN113214254B CN202110385304.4A CN202110385304A CN113214254B CN 113214254 B CN113214254 B CN 113214254B CN 202110385304 A CN202110385304 A CN 202110385304A CN 113214254 B CN113214254 B CN 113214254B
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- hole
- host material
- organic electroluminescent
- electroluminescent device
- transport
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- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 claims description 2
- WCXKTQVEKDHQIY-UHFFFAOYSA-N 3-[3-[3-(3,5-dipyridin-3-ylphenyl)phenyl]-5-pyridin-3-ylphenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=C(C=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=NC=CC=2)C=2C=NC=CC=2)=C1 WCXKTQVEKDHQIY-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
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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
- 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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Abstract
The invention belongs to the technical field of organic photoelectric materials, and discloses a hole-transport type main body material, a preparation method thereof and application thereof in preparation of organic electroluminescent devices. The hole-transport type main body material has a structural formula shown in a formula (I). The hole transport material has good hole transport capability, can be applied to a hole layer of an organic electroluminescent device or combined with an electron transport type material to form an exciplex to be used as a luminescent layer or a main material in the luminescent layer, and realizes higher device efficiency. The hole transport material has higher stability, can be applied to an exciplex main body, and effectively realizes an electroluminescent device with longer service life.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a hole-transport-type main body material, a preparation method thereof and application thereof in preparation of organic electroluminescent devices.
Background
Organic Light-Emitting diodes (OLEDs) are attracting attention because they exhibit advantages of lightness, thinness, energy saving, self-luminescence, wide color gamut, and the like, which are superior to those of conventional display technologies, in practical applications. Through rapid development for over thirty years, the OLED gradually becomes the forefront of the display technology and is successfully applied to small and medium-sized display products such as notebook computers, smart phones and smart bracelets. However, the OLED has not been able to completely replace the conventional display technology so far, and one reason for this is the insufficient performance of the organic electroluminescent material. Therefore, the development of efficient and stable organic electroluminescent materials and peripheral materials thereof is significant.
Design strategies for doping guest materials into host materials are often employed in organic electroluminescent devices to achieve higher device efficiencies and longer device lifetimes. According to the strategy, mutual collision between excitons of the luminescent guest is effectively avoided by dispersing guest molecules, the concentration quenching effect is inhibited, energy dissipation caused by mutual collision of the excitons is reduced, device roll-off of the device under high brightness is inhibited, and the efficiency and the service life of the device are effectively promoted. Common single host materials generally have strong hole transporting capacity, but have poor bipolar transporting capacity, which easily causes the imbalance of carriers in the device, and causes the serious roll-off of the device efficiency under high brightness and the short service life of the device. The novel exciplex main body system developed by J.H.Kwon and J.J.Kim, etc. can better solve the defects of the traditional single main body material. The exciplex host is generally formed of one hole-transporting host material (P-type host) and one electron-transporting host material (N-type host). Δ E of the exciplex host due to the fully separated highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO) ST The material is often small, so that the appropriate triplet state energy level which should be provided as a host material is ensured, and the energy level of the host material can be flexibly coordinated so as to reduce the driving voltage. In addition, by adjusting the proportion of the P-type main body and the N-type main body, the balance of current carriers can be flexibly adjusted, the external quantum efficiency of the device is effectively improved, and the service life of the device is prolonged. Green devices based on exciplex hosts reported as taught by the Kim professor 2014 have efficiencies as high as 32.3%. (adv.mater.2014,26,3844)
However, the working life of the devices based on the exciplex host generally fails to meet the requirements of commercial applications, and particularly, the types of the stable exciplex host for the thermally activated delayed fluorescence guest material are few, the chemical structure stability of the host material is insufficient, and the device performance and the lifetime thereof are yet to be further optimized and improved. The main problem of the exciplex host material is that high-energy excitons and high-density carriers are continuously generated during the operation of the device, so that the unstable P-type host material is subjected to the risks of molecular chemical bond cracking and material aging attenuation, and the brightness and the efficiency of the device are attenuated. Especially, the bond cleavage reaction of C-N bond of aromatic amine material is a common aging source. Therefore, the design of the more stable and efficient P-type main body material is beneficial to promoting the further application and popularization of the exciplex main body, so that the efficiency and the service life of the electroluminescent device are improved, and the commercialization process of the organic electroluminescent device is promoted.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a high-efficiency and stable hole-transport type main body material.
Another object of the present invention is to provide a method for producing the above hole transport host material.
Still another object of the present invention is to form a matrix host using the above hole transport host material for highly efficient and stable organic photoelectric devices.
The purpose of the invention is realized by the following technical scheme:
a hole-transporting host material has a general structural formula shown in formula (I):
wherein Ar is
Preferably, the molecular structure of the hole transport type host material is the following H 1 ～H 14 Any one of:
the preparation method of the hole-transport-type main body material comprises the following steps:
under the conditions of a palladium catalyst and alkali, carrying out Suzuki coupling reaction on a compound with a structural general formula shown in a formula (II) and Ar-Br to obtain the hole-transport type main body material;
preferably, the reaction temperature of the suzuki coupling reaction is 80-85 ℃.
Preferably, the base comprises potassium carbonate, sodium carbonate, cesium carbonate, lithium carbonate.
Preferably, the palladium catalyst comprises tetrakis (triphenylphosphine) palladium, palladium acetate, bis (tri-tert-butylphosphine) palladium, palladium pivalate, palladium trifluoroacetate and palladium on carbon.
The application of the hole-transporting host material in preparing electroluminescent devices.
Preferably, the hole transport type host material is used as a hole transport layer.
Preferably, the hole transport type host material and the electron transport material form an exciplex as a host material in the light emitting layer or the light emitting layer. More preferably, the molecular structure of the electron transport material is any one of the following SF3-TRZ, T2T, TmPyPB, B3PyPB, B3PyMPM and B4 PYMPM:
the principle of the invention is as follows: most of common hole-transport host molecules are designed based on phenyl carbazole groups, and the exposed carbon-nitrogen bond between carbazole and a benzene ring in the carbazole groups is often low in chemical bond energy and becomes a defect site in the working process of a device. Compared with the conventional hole-transport type host material designed based on phenyl carbazole, the series of hole-transport type host materials protect originally weaker carbon-nitrogen bonds by fusing carbazole and 9-position phenyl connected with carbazole into rings, the carbazole groups and benzene rings are subjected to cyclization to make the carbazole groups and the benzene rings planarized together, and conjugated electron clouds are favorable for improving the chemical bond energy of the carbon-nitrogen bonds. The common spiro structure is beneficial to improving the rigidity in molecules and reducing the proportion of non-radiative transition. In addition, due to the strong rigid structure of the molecule, different modifying groups are introduced to enhance the hole transmission capability of the main material and coordinate the energy level and energy of the hole type main material. The organic electroluminescent device made of the series of hole-transport type main body materials has higher device efficiency and longer device service life.
The organic micromolecule luminescent material and the organic electroluminescent device have the following advantages and beneficial effects:
(1) compared with the conventional host molecule designed based on a phenylcarbazole unit, the hole-transport-type host material disclosed by the invention has the advantages that an originally weaker carbon-nitrogen bond is protected in a ring fusion mode, the co-planarization of phenyl and carbazole is enhanced in a cyclization mode, and conjugated electron cloud is beneficial to improving the chemical bond energy of the carbon-nitrogen bond, so that the stability of an electroluminescent device is improved;
(2) the hole-transport type main material has good hole-transport capability and higher triplet state energy level, can be applied to a hole-transport layer of an organic electroluminescent device, and can also be combined with a commonly used electron-transport type main material to form an exciplex main body, so that the carrier balance in a light-emitting layer can be more flexibly coordinated
(3) The hole-transport type main material can flexibly regulate and control the single triplet state energy level, the front line track distribution and the hole transport capacity of the material by changing the types and modification sites of the modification groups connected with the material, so that the material meets the requirements of different electroluminescent devices;
(4) the hole-transport-type main body material has the advantages of large and definite molecular weight and strong molecular rigidity, and endows the main body material with higher thermal stability and proper sublimation temperature, thereby facilitating purification;
(5) the hole-transport-type main body material system is successfully applied to the electroluminescent device with thermally activated delayed fluorescence, and the all-organic electroluminescent device is prepared. The exciplex system not only realizes the flexible adjustment of the carrier balance, but also effectively reduces unstable factors in the system by using the short excitons of the exciplex main body, and improves the stability of the electroluminescent device based on thermal activation delayed fluorescence.
Drawings
FIG. 1 is a graph of current density-voltage-luminance relationship of organic electroluminescent devices of examples 15 and 16;
FIG. 2 is a graph showing luminance-external quantum efficiency relationship between organic electroluminescent devices of examples 15 and 16;
FIG. 3 shows the current density of 1mA cm/cm for the organic electroluminescent devices of examples 15 and 16 -2 Electroluminescence spectrum of time;
FIG. 4 is a graph showing a current density-voltage-luminance relationship of organic electroluminescent devices of examples 17 and 18;
FIG. 5 is a graph showing luminance-external quantum efficiency relationships of organic electroluminescent devices of examples 17 and 18;
FIG. 6 is a graph showing the current density of 1mA cm in organic electroluminescent devices of examples 17 and 18 -2 Electroluminescence spectrum of time;
FIG. 7 is a graph showing a current density-voltage-luminance relationship between organic electroluminescent devices of examples 24 and 25;
FIG. 8 is a graph showing luminance-external quantum efficiency relationships of organic electroluminescent devices of examples 24 and 25;
FIG. 9 shows the organic electroluminescent devices of example 24 and example 25 at a current density of 1mA cm -2 Electroluminescence spectrum of time;
FIG. 10 is a graph of luminance-continuous operation time relationship curves of organic electroluminescent devices of examples 24 and 25 and a curve fitted thereto (fit);
FIG. 11 is a graph of current density-voltage-luminance relationships for organic electroluminescent devices of example 26, example 27 and example 28;
FIG. 12 is a graph showing luminance-external quantum efficiency relationships of the organic electroluminescent devices of example 26, example 27 and example 28;
FIG. 13 shows the current densities of 1mA cm and cm for the organic electroluminescent devices of example 26, example 27 and example 28 -2 Electroluminescence spectrum of time;
FIG. 14 is a graph of luminance-continuous operation time relationship curves of organic electroluminescent devices of example 26, example 27 and example 28 and a curve fitted thereto (fit);
FIG. 15 shows an example 26 of a guest material 4CzIPN having an ultraviolet-visible absorption spectrum and a hole transporting host material H 1 Emission spectra of the film, the electron transport material T2T film, and a film blended with the two in a ratio of 2: 8.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
Hole-transport-type host material H 1 The preparation method comprises the following preparation steps:
intermediate M 4 The reaction formula (2) is as follows:
the specific reaction steps are as follows:
intermediate M 1 The synthesis of (2): in a 250mL three-necked flask containing nitrogen, 10g (59.8mmol) of carbazole, 16.93g (71.77mmol) of o-dibromobenzene, 3g (0.016mmol) of cuprous oxide, 41.32g (299mmol) of potassium carbonate, and 2.16g (11.96mmol) of 1, 10-phenanthroline were thoroughly mixed and dissolved in 100mL of a dimethylformamide solution. The system was heated to 155 ℃ and stirred for 24 hours. After the reaction is finished, when the system is cooled to room temperature, the system is diluted by about 250ml of dichloromethane solution, and then the salt in the system is removed by decompression and suction filtration. Vacuum evaporating the organic solvent to remove excessive solvent, extracting with dichloromethane and saturated saline solution for several times, and vacuum evaporating the obtained organic phaseTo a viscous liquid. Column chromatography using a silica gel column about 45cm high gave 7.93g (41% yield) of a pale yellow viscous liquid. Intermediate M 1 The molecular formula (II) is as follows: c 18 H 12 BrN; molecular weight: m/z: 321.02, respectively; the elemental analysis results were: c, 67.10; h, 3.75; br, 24.80; and N, 4.35.
Intermediate M 2 The synthesis of (2): in a 250mL three-necked flask under nitrogen atmosphere, 3g (9.31mmol) of intermediate M was charged 1 Fully dissolved in 120ml of anhydrous tetrahydrofuran solution, precooled for 30 minutes at-78 ℃, then dropwise added with 4.1ml (10.24mmol) of n-hexane solution of 2.5mmol/ml n-butyllithium, and stirred for reaction for 1 hour under the environment of-78 ℃. Thereafter, 2.53g (9.78mmol) of 3-bromo-9-fluorenone was dissolved in 50ml of an anhydrous tetrahydrofuran solution, and it was slowly added to the reaction system. Then, the system is gradually heated to the room temperature, and the reaction is continuously stirred for 8 hours. After the reaction is finished, dilute hydrochloric acid and dichloromethane are used for extracting for many times, and the lower layer organic phase is taken out and evaporated to spin dry the solvent under reduced pressure. Column chromatography using a silica gel column about 30cm high gave 4.43g (95% yield) of a white solid. Intermediate M 2 The molecular formula (II) is as follows: c 31 H 20 BrNO; molecular weight: m/z: 501.07; the elemental analysis results were: c, 74.11; h, 4.01; br, 15.90; n, 2.79; and O, 3.18.
Intermediate M 3 The synthesis of (2): in a 250mL three-necked flask under nitrogen, 4g (7.94mmol) of intermediate M was placed 2 Uniformly mixing the mixture in 130ml of glacial acetic acid solution, heating the mixture to 120 ℃ until the mixture is completely dissolved, adding 5ml of hydrochloric acid into the system, and continuously stirring the mixture for reaction for 24 hours. After the reaction is finished, cooling the system to room temperature, carrying out vacuum filtration to obtain dark green liquid, and carrying out vacuum evaporation to spin-dry the solvent. Column chromatography using a silica gel column about 25cm high gave 1.86g (96% yield) of an off-white solid. Intermediate M 3 The molecular formula (1): c 31 H 18 BrN; molecular weight: m/z: 483.06; the elemental analysis results were: c, 76.87; h, 3.75; br, 16.50; and N, 2.89.
Intermediate M 4 The synthesis of (2): in a 250mL three-necked flask under nitrogen atmosphere, 2.5g (5.16mmol) of intermediate M was introduced 3 Fully dissolved in 75ml of anhydrous tetrahydrofuran solution at-78 DEG CAfter cooling for 30 minutes, 3.1ml (7.74mmol) of an n-hexane solution of 2.5mmol/ml n-butyllithium was added dropwise thereto, and the reaction was stirred at-78 ℃ for 1 hour. Thereafter, 1.92g (10.32mmol) of 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborane was injected into the system by syringe. Then, the system is gradually heated to the room temperature, and the reaction is continuously stirred for 8 hours. After the reaction was completed, the solvent was directly evaporated under reduced pressure, and the residue was separated by means of a silica gel column chromatography having a height of about 25cm to obtain 1.91g (yield: 73%) of a yellow solid. Intermediate M 4 The molecular formula (II) is as follows: c 37 H 30 BNO 2 (ii) a Molecular weight: m/z: 531.24; the elemental analysis results were: c, 83.62; h, 5.69; b, 2.03; n, 2.64; and O, 6.02.
Hole transport type host material H 1 The synthesis reaction formula (2) is as follows:
the specific reaction steps are as follows:
in a 250mL three-necked flask under nitrogen atmosphere, 1.82g (3.76mmol) of intermediate M was charged 3 2g (3.76mmol) of intermediate M 4 Then, 9.4ml (18.8mmol) of an aqueous solution of 2mmol/ml potassium carbonate was uniformly mixed with 120ml of a toluene/methanol mixed solvent (toluene: methanol ═ 5: 1). 0.22g (0.19mmol) of tetrakis (triphenylphosphine) palladium was added to the system under sufficient nitrogen protection, and then the system was heated to 83 ℃ to stir the reaction for 24 hours. After the reaction is finished, cooling the system to room temperature, carrying out reduced pressure suction filtration to remove the metal palladium in the system, and evaporating the obtained liquid to dry the solvent in a spinning way under reduced pressure. Column chromatography using a silica gel column about 30cm high gave 2.56g (84% yield) of a white solid. H 1 The molecular formula (II) is as follows: c 62 H 36 N 2 (ii) a Molecular weight: m/z: 808.29, respectively; the elemental analysis results were: c, 92.05; h, 4.49; and N, 3.46.
Example 2
Hole-transport-type host material H 2 The preparation method comprises the following preparation steps:
hole transport type host material H 2 The synthetic reaction formula is asShown below:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M 3 By replacement with equivalent amounts of 2- (4-bromophenyl) -1-phenyl-1H-phenanthro [9,10-d]Imidazole, other raw materials and procedures are the same as those of the hole transport type host material H 1 The synthesis reaction of (1). Finally obtaining the hole-transporting type main body material H 2 The yield was 65%. H 2 The molecular formula (II) is as follows: c 58 H 35 N 3 (ii) a Molecular weight: m/z: 773.28; the elemental analysis results were: c, 90.01; h, 4.56; n, 5.43. .
Example 3
Hole-transport-type host material H 3 The preparation method comprises the following preparation steps:
intermediate M 6 The reaction formula (2) is as follows:
the specific reaction steps are as follows:
intermediate M 5 The synthesis of (2): in a 250mL three-necked flask under a nitrogen atmosphere, 6.6g of 2- (methylthio) phenylboronic acid (38.9mmol), 10.0g of 5-chloro-3-iodopyridin-2-amine (38.9mmol), 16.3g of potassium borate (117mmol) were sufficiently dissolved in a 180mL of tetrahydrofuran and 60mL of distilled water mixed solution and stirred uniformly. Under sufficient nitrogen protection, 1.26g (1.17mmol) of tetrakis (triphenylphosphine) palladium was added to the system, and the mixture was refluxed for 24 hours. The system was then cooled to room temperature and extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous magnesium sulfate and evaporated in vacuo to give a crude product which was purified by column chromatography on silica gel using hexane/ethyl acetate solution as eluent to give 6.7g of intermediate M 5 . The yield was 69%. Intermediate M 5 The molecular formula (1): c 12 H 11 ClN 2 S; molecular weight: m/z: 250.03; the elemental analysis results were: c, 57.48; h, 4.42; cl, 14.14; n, 11.17; s, 12.79.
Intermediate M 6 The synthesis of (2): 6.5g of 5-chloro-3- (2- (methylthiophenyl) phenyl) pyridin-2-amine (25.9mmol) were thoroughly mixed in 39ml of tetrahydrofuran and 65ml of glacial acetic acid at-10 ℃ and 9.4g of butyl nitrite (90.8mmol) were added via syringe over 10 minutes, stirred at-10 ℃ for 1 hour and subsequently heated to 0 ℃ and the reaction stirred for 12 hours. After the reaction is finished, the reaction system is heated to room temperature and extracted by ethyl acetate and deionized water. The organic layer was dried over anhydrous magnesium sulfate and evaporated in vacuo to give the crude product, which was purified by silica gel column chromatography using hexane/ethyl acetate as eluent to give 3.2g of intermediate M 6 . The yield was 61%. Intermediate M 6 The molecular formula (1): c 11 H 6 ClNS; molecular weight: m/z: 218.99, respectively; the elemental analysis results were: c, 60.14; h, 2.75; cl, 16.14; n, 6.38; s, 14.59.
Hole transport host material H 3 The synthesis reaction formula (2) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M 3 By conversion to intermediate M 6 Other materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (1). Finally obtaining the hole-transporting type host material H 3 The yield was 66%. H 3 The molecular formula (1): c 42 H 24 N 2 S; molecular weight: m/z: 588.17, respectively; the elemental analysis results were: c, 85.69; h, 4.11; n, 4.76; and S, 5.45.
Example 4
Hole-transport-type host material H 4 The preparation method comprises the following preparation steps:
intermediate M 7 The reaction formula (c) is as follows:
the specific reaction steps are as follows:
a dried 200ml Schlenk tube was charged with 2.50g of 2-mercaptobenzimidazole (16.64mmol), 4.91g of 2, 5-dibromo-1-nitrobenzene (17.48mmol), 16.26g of cesium carbonate (49.92mmol) and 30ml of anhydrous dimethyl sulfoxide. The reaction mixture was heated to 120 ℃ under argon atmosphere and stirred well for 1 hour, then heated to 180 ℃ and stirred for another 2 hours. After cooling to room temperature, the reaction mixture was diluted with 30ml of deionized water and extracted three times with 50ml of chloroform solvent. The combined organic extracts were dried over sodium sulfate and concentrated by rotary evaporation. The crude product was purified by column purification silica gel chromatography using 1:3 chloroform/petroleum ether as eluent to give a white solid (3.82g) in 76% yield. Intermediate M 7 The molecular formula (II) is as follows: c 13 H 7 BrN 2 S; molecular weight: m/z: 301.95; the elemental analysis results were: c, 51.50; h, 2.33; br, 26.36; n, 9.24; s, 10.57.
Hole transport host material H 4 The synthetic reaction formula of (a) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M 3 By conversion to intermediate M 7 The other raw materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (2). Finally obtaining the hole-transporting type main body material H 4 The yield was 66%. H 4 The molecular formula (II) is as follows: c 44 H 25 N 3 S; molecular weight: m/z: 627.18, respectively; the elemental analysis results were: c, 84.19; h, 4.01; n, 6.69; and S, 5.11.
Example 5
Hole-transport-type host material H 5 The preparation method comprises the following preparation steps:
intermediate M 9 The reaction formula (c) is as follows:
the specific reaction steps are as follows:
intermediate M 8 The synthesis of (2): with intermediate M 2 Except that intermediate M is prepared 1 The equivalent 2-bromo-1, 1' -biphenyl is replaced, and other raw materials and steps are the same as those of the intermediate M 2 To finally obtain an intermediate M 8 The yield was 90%. Intermediate M 8 The molecular formula (II) is as follows: c 25 H 17 BrO; molecular weight: m/z: 412.05; the elemental analysis results were: c, 72.65; h, 4.15; br, 19.33; o, 3.87.
Intermediate M 9 The synthesis of (2): with intermediate M 3 Except that intermediate M is prepared 2 By replacement with an equivalent amount of intermediate M 8 Other raw materials and steps are the same as those of the intermediate M 3 To finally obtain an intermediate M 9 The yield was 92%. Intermediate M 9 The molecular formula (1): c 25 H 15 Br; molecular weight: m/z: 394.04, respectively; the elemental analysis results were: c, 75.96; h, 3.82; br, 20.21.
Hole transport host material H 5 The synthetic reaction formula of (a) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M 3 By conversion to intermediate M 9 Other materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (2). Finally obtaining the hole-transporting type host material H 5 The yield was 68%. H 5 Of the formula：C 56 H 33 N; molecular weight: m/z: 719.26; the elemental analysis results were: c, 93.43; h, 4.62; and N, 1.95.
Example 6
Hole-transport-type host material H 6 The preparation method comprises the following preparation steps:
intermediate M 12 The reaction formula (c) is as follows:
intermediate M 10 The synthesis of (2): with intermediate M 2 The difference is that 3-bromo-9-fluorenone is changed into 2-bromo-9-fluorenone with equivalent weight, and other raw materials and steps are the same as the intermediate M 2 To finally obtain the offwhite intermediate M 10 The yield was 93%. Intermediate M 10 The molecular formula (II) is as follows: c 31 H 20 BrNO; molecular weight: m/z: 501.07; the elemental analysis results were: c, 74.11;
H,4.01；Br,15.90；N,2.79；O,3.18。
intermediate M 11 The synthesis of (2): with intermediate M 3 Except that intermediate M is reacted in the presence of a catalyst 2 By replacement with an equivalent amount of intermediate M 10 Other raw materials and steps are the same as those of the intermediate M 3 To finally obtain a white intermediate M 11 The yield was 95%. Intermediate M 11 The molecular formula (1): c 31 H 18 BrN; molecular weight: m/z: 483.06, respectively; the elemental analysis results were: c, 76.87; h, 3.75; br, 16.50; and N, 2.89.
Intermediate M 12 The synthesis of (2): with intermediate M 4 Except that intermediate M is reacted in the presence of a catalyst 3 By replacement with an equivalent amount of intermediate M 11 Other raw materials and steps are the same as those of the intermediate M 4 To finally obtain a yellow intermediate M 12 The yield was 68%. Intermediate M 12 The molecular formula (II) is as follows: c 37 H 30 BNO 2 (ii) a Molecular weight: m/z: 531.24; the elemental analysis results were: c, 83.62; h, 5.69; b, the content of the first and second polymers is determined,2.03；N,2.64；O,6.02。
hole transport type host material H 6 The synthesis reaction formula (2) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M 3 And intermediate M 4 Respectively exchanged into an intermediate M 11 And intermediate M 12 The other raw materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (2). Finally obtaining the hole-transporting type main body material H 6 The yield was 65%. H 6 The molecular formula (1): c 62 H 36 N 2 (ii) a Molecular weight: m/z: 808.29, respectively; the elemental analysis results were: c, 92.05; h, 4.49; and N, 3.46.
Example 7
Hole-transport-type host material H 7 The preparation method comprises the following preparation steps:
hole transport host material H 7 The synthesis reaction formula (2) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M is 3 And intermediate M 4 Respectively exchanged into an equivalent intermediate M 12 And 2- (4-bromophenyl) -1-phenyl-1H-phenanthro [9,10-d]Imidazole, other raw materials and procedures are the same as those of the hole transport type host material H 1 The synthesis reaction of (2). Finally obtaining the hole-transporting type main body material H 7 The yield was 63%. H 7 The molecular formula (1): c 58 H 35 N 3 (ii) a Molecular weight: m/z: 773.28, respectively; the elemental analysis results were: c, 90.01; h, 4.56; n, 5.43.
Example 8
Hole-transport-type host material H 8 The preparation method comprises the following preparation steps:
hole transport type host material H 8 The synthesis reaction formula (2) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M is 3 And intermediate M 4 Respectively exchanged into an intermediate M 6 And intermediate M 12 Other materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (1). Finally obtaining the hole-transporting type main body material H 8 The yield was 66%. H 8 The molecular formula (1): c 42 H 24 N 2 S; molecular weight: m/z: 588.17, respectively; the elemental analysis results were: c, 85.69; h, 4.11; n, 4.76; and S, 5.45.
Example 9
Hole-transport-type host material H 9 The preparation method comprises the following preparation steps:
hole transport host material H 9 The synthetic reaction formula of (a) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M is 3 And intermediate M 4 Respectively exchanged into an intermediate M 7 And intermediate M 12 The other raw materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (1). Finally obtaining the hole-transporting type main body material H 9 The yield was 67%. H 9 The molecular formula (1): c 44 H 25 N 3 S; molecular weight: m/z: 627.18; the elemental analysis results were: c, 84.19; h, 4.01; n, 6.69; and S, 5.11.
Example 10
Hole-transport-type host material H 10 The preparation method comprises the following preparation steps:
hole transport type host material H 10 The synthetic reaction formula of (a) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M 3 And intermediate M 4 Respectively exchanged into an intermediate M 9 And intermediate M 12 Other materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (2). Finally obtaining the hole-transporting type main body material H 10 The yield was 63%. H 10 The molecular formula (II) is as follows: c 56 H 33 N; molecular weight: m/z: 719.26; the elemental analysis results were: c, 93.43; h, 4.62; and N, 1.95.
Example 11
Hole-transport-type host material H 11 The preparation method comprises the following preparation steps:
intermediate M 15 The reaction formula (2) is as follows:
the specific reaction steps are as follows:
intermediate M 13 The synthesis of (2): with intermediate M 2 The difference is that 3-bromo-9-fluorenone is changed into 4-bromo-9-fluorenone with equivalent weight, and other raw materials and steps are the same as the intermediate M 2 To finally obtain the off-white intermediate M 13 The yield was 68%. Intermediate M 13 The molecular formula (1):C 31 H 20 BrNO; molecular weight: m/z: 501.07; the elemental analysis results were: c, 74.11; h, 4.01; br, 15.90; n, 2.79; and O, 3.18.
Intermediate M 14 The synthesis of (2): with intermediate M 3 Except that intermediate M is reacted in the presence of a catalyst 2 By replacement with an equivalent amount of intermediate M 13 Other raw materials and steps are the same as those of the intermediate M 3 To finally obtain a white intermediate M 14 The yield was 65%. Intermediate M 14 The molecular formula (II) is as follows: c 31 H 18 BrN; molecular weight: m/z: 483.06; the elemental analysis results were: c, 76.87; h, 3.75; br, 16.50; and N, 2.89.
Intermediate M 15 The synthesis of (2): with intermediate M 4 Except that intermediate M is prepared 3 By replacement with an equivalent amount of intermediate M 14 The other raw materials and steps are the same as those of the intermediate M 3 To finally obtain a yellow intermediate M 12 The yield was 68%. Intermediate M 12 The molecular formula (1): c 37 H 30 BNO 2 (ii) a Molecular weight: m/z: 531.24; the elemental analysis results were: c, 83.62; h, 5.69; b, 2.03; n, 2.64; and O, 6.02.
Hole transport host material H 11 The synthetic reaction formula of (a) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M 3 And intermediate M 4 Respectively exchanged into an equivalent intermediate M 15 And 2- (4-bromophenyl) -1-phenyl-1H-phenanthro [9,10-d]Imidazole, other raw materials and procedures are the same as those of the hole transport type host material H 1 The synthesis reaction of (1). Finally obtaining the hole-transporting type main body material H 11 The yield was 57%. H 11 The molecular formula (II) is as follows: c 58 H 35 N 3 (ii) a Molecular weight: m/z: 773.28; the elemental analysis results were:C,90.01；H,4.56；N,5.43。
example 12
Hole-transport-type host material H 12 The preparation method comprises the following preparation steps:
hole transport type host material H 12 The synthetic reaction formula of (a) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M 3 And intermediate M 4 Respectively exchanged into an intermediate M 6 And intermediate M 15 Other materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (1). Finally obtaining the hole-transporting type main body material H 12 The yield was 55%. H 12 The molecular formula (1): c 42 H 24 N 2 S; molecular weight: m/z: 588.17; the elemental analysis results were: c, 85.69; h, 4.11; n, 4.76; and S, 5.45.
Example 13
Hole-transport-type host material H 13 The preparation method comprises the following preparation steps:
hole transport host material H 13 The synthesis reaction formula (2) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M is 3 And intermediate M 4 Respectively exchanged into an intermediate M 7 And intermediate M 15 The other raw materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (2). Finally obtaining the hole-transporting type main body material H 13 The yield was 53%. H 13 The molecular formula (1): c 44 H 25 N 3 S; molecular weight: m/z: 627.18, respectively; the elemental analysis results were: c, 84.19; h, 4.01; n, 6.69; and S, 5.11.
Example 14
Hole-transport-type host material H 14 The preparation method comprises the following preparation steps:
hole transport type host material H 14 The synthesis reaction formula (2) is as follows:
the specific reaction steps are as follows:
and a hole transport type host material H 1 Compared with the synthesis reaction, the difference lies in that the intermediate M is 3 And intermediate M 4 Respectively exchanged into an intermediate M 9 And intermediate M 15 The other raw materials and steps are the same as those of the hole transport type host material H 1 The synthesis reaction of (1). Finally obtaining the hole-transporting type host material H 14 The yield was 54%. H 14 The molecular formula (II) is as follows: c 56 H 33 N; molecular weight: m/z: 719.26, respectively; the elemental analysis results were: c, 93.43; h, 4.62; and N, 1.95.
Example 15
An organic electroluminescent device takes SF3-TRZ as a main body of a light-emitting layer, and the structure of the organic electroluminescent device is as follows:
ITO(95nm)/4％F6-TCNNQ:NPB(50nm)/H 1 (10nm)/10％4CzIPN:SF3-TRZ(30nm)/SF3-TRZ(10nm)/50％Liq:NBPhen(40nm)/LiF(1nm)/Al(100nm)
wherein, the transparent ITO is used as an anode, the NPB is used as a hole transport layer, the hole transport layer is doped with F-TCNNQ with the mass concentration of 4 percent, and the hole transport type main body material H is used 1 (H 1 Hole transport host material H prepared for example 1 1 (ii) a The following H 1 -H 14 The same principle) is an electron blocking layer, the thermal activation delayed fluorescence material 4CzIPN with the mass concentration of 10% is taken as a light-emitting object in the light-emitting layer, and SF3-TRZ is taken as a light-emitting layer host and voidThe hole blocking layer is a blending system doped into NBPhen by 50% Liq and used as an electron transport layer, LiF is used as an electron injection layer, and Al is used as a metal cathode.
The structural formula of the material used in the organic electroluminescent device of this example is as follows:
the electroluminescent device of this example was prepared as follows:
and (2) carrying out ultrasonic cleaning on the ITO-etched conductive glass substrate by deionized water, tetrahydrofuran, a washing solution, deionized water and isopropanol in sequence to remove organic impurities, water-soluble impurities and possibly residual photoresist on the surface of the substrate, and then putting the substrate into an electrothermal blowing drying oven to dry for more than 3 hours to remove solvent residues. Then taking out the dried ITO substrate, carrying out plasma treatment for 10 minutes, then conveying the ITO substrate into a vacuum evaporation chamber, and pumping until the vacuum degree is lower than 10 -4 Pa. And depositing organic materials on the ITO substrate to form a film in sequence through vacuum evaporation, wherein the doping proportion of the doping layer is regulated and controlled through a certain deposition rate proportion. Finally, metal aluminum is evaporated to be uniformly covered on the organic material layer, and the organic electroluminescent device of the embodiment is obtained.
The organic electroluminescent device of the present example was evaluated in the following manner:
the current density-voltage-luminance characteristic curve of the electroluminescent device was measured by a combination of a color luminance meter CS-200 (konidamida) -Keithley-2400 (gishley) programmable voltage-current source meter. The electroluminescence spectra of the electroluminescent devices were measured by a fiber optic spectrometer USB2000+ (marine optics) under different current density driving conditions of Keithley-2400.
The organic electroluminescent device of the present example had a current density-voltage-luminance relationship, a luminance-external quantum efficiency relationship, and a luminance at a current density of 1mA cm -2 The electroluminescence spectra are shown in FIG. 1, FIG. 2 and FIG. 3, respectively. The photoelectric property data are shown in table 1.
Example 16
An organic electroluminescent device comprises an exciplex as the main body of luminescent layer, wherein the main body of exciplex is made of hole-transporting main material H 1 The organic electroluminescent device is blended with an electron transport type host material SF3-TRZ according to the proportion of 2:8, and the organic electroluminescent device has the following structure:
ITO(95nm)/4％F6-TCNNQ:NPB(50nm)/H 1 (10nm)/10％4CzIPN:18％H 1 :72％SF3-TRZ(30nm)/SF3-TRZ(10nm)/50％Liq:NBPhen(40nm)/LiF(1nm)/Al(100nm)
among them, the difference from example 15 is that the thermally activated delayed fluorescence material 4CzIPN having a mass concentration of 10% is used as a light emitting guest in the light emitting layer, and 18% of the hole transport type host material H 1 72% SF3-TRZ is the host for exciplex. The remaining device structure, device fabrication steps and performance evaluation were the same as in example 15.
The organic electroluminescent device of the present example had a current density-voltage-luminance relationship, a luminance-external quantum efficiency relationship, and a luminance at a current density of 1mA cm -2 The electroluminescence spectra are shown in FIG. 1, FIG. 2 and FIG. 3, respectively. The photoelectric property data are shown in table 1.
TABLE 1 optoelectronic Performance data of the organic opto-electronic devices of examples 15 and 16
a Luminance of 1cd m -2 A driving voltage of time; b Current Density of 1mA cm -2 Electroluminescence of time
As can be seen from the above data, example 15 has the same emission peak and identical CIE color coordinates as example 16, meaning that the emission peaks are both from the radiative emission of the 4CzIPN guest material. Compared with example 15, example 16 has lower turn-on voltage (2.9V) and higher maximum external quantum efficiency (23.48%) and represents that the hole transport type host material H is used as the base material 1 Electric of exciplex host formed with electron transport material SF3-TRZA great advantage of the electroluminescent device. The organic electroluminescent device based on the exciplex effectively reduces the turn-on voltage of the device by utilizing the energy level structure of the exciplex main body which is better matched, and simultaneously coordinates the carrier balance in the electroluminescent device through proper proportion to show the hole-transport type main body material H 1 The application is excellent.
Example 17
The difference from example 15 is that the host materials SF3-TRZ in the light-emitting layer were replaced with hole transporting host material H 1 The electron transport material SF3-TRZ in the hole blocking layer is changed into the electron transport material T2T, and the doping ratio is not changed. The remaining device structure, device fabrication steps, and performance evaluation were the same as in example 15.
The structural formula of the electron transport host material T2T used in the organic electroluminescent device of this example is as follows:
the organic electroluminescent device of the present example had a current density-voltage-luminance relationship, a luminance-external quantum efficiency relationship, and a luminance at a current density of 1mA cm -2 The electroluminescence spectra at the time are shown in FIG. 4, FIG. 5 and FIG. 6, respectively. The photoelectric property data are shown in table 2.
Example 18
Compared with example 16, the difference is that the electron transport material SF3-TRZ in the light-emitting layer and the hole blocking layer is replaced by the electron transport material T2T, and the doping ratio is not changed. The remaining device structures were the same as in example 16. The device fabrication procedure and performance evaluation were the same as in example 15.
The organic electroluminescent device of the present example had a current density-voltage-luminance relationship chart, a luminance-external quantum efficiency relationship chart, and a luminance at a current density of 1mA cm -2 The electroluminescence spectra at the time are shown in FIG. 4, FIG. 5 and FIG. 6, respectively. The photoelectric property data are shown in table 2.
Example 19
The difference from example 16 is that the electron transport material SF3-TRZ in the light-emitting layer and the hole-blocking layer was changed to the electron transport material T2T, and the hole transport host material H in the electron-blocking layer 1 By changing to hole-transporting host material H 6 Hole transport type host material H in light-emitting layer 1 By substituting hole-transporting host material H 6 The doping ratio is unchanged. The remaining device structures were the same as in example 16. The device fabrication procedure and performance evaluation were the same as in example 15.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 2.
Example 20
The difference from example 16 is that the electron transport material SF3-TRZ in the light-emitting layer and the hole-blocking layer was changed to the electron transport material T2T, and the hole transport host material H in the electron-blocking layer 1 By substituting hole-transporting host material H 7 Hole transport type host material H in light-emitting layer 1 By substituting hole-transporting host material H 7 The doping ratio is unchanged. The remaining device structures were the same as in example 16. The device fabrication procedure and performance evaluation were the same as in example 15.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 2.
Example 21
The difference from example 16 is that the electron transport material SF3-TRZ in the light-emitting layer and the hole-blocking layer was changed to the electron transport material T2T, and the hole transport host material H in the electron-blocking layer 1 By substituting hole-transporting host material H 8 Hole transport host material H in the light-emitting layer 1 By changing to hole-transporting host material H 8 The doping ratio is unchanged. The remaining device structures were the same as in example 16. The device fabrication procedure and performance evaluation were the same as in example 15.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 2.
Example 22
The difference from example 16 is that the electron transport material SF3-TRZ in the light-emitting layer and the hole-blocking layer was replaced with an electron transport material T2T, and the hole transport host material H in the electron-blocking layer 1 By substituting hole-transporting host material H 9 Hole transport host material H in the light-emitting layer 1 By substituting hole-transporting host material H 9 The doping ratio is unchanged. The remaining device structures were the same as in example 16. The device fabrication procedure and performance evaluation were the same as in example 15.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 2.
Example 23
The difference from example 16 is that the electron transport material SF3-TRZ in the light-emitting layer and the hole-blocking layer was changed to the electron transport material T2T, and the hole transport host material H in the electron-blocking layer 1 By changing to hole-transporting host material H 10 Hole transport type host material H in light-emitting layer 1 By changing to hole-transporting host material H 10 The doping ratio is unchanged. The remaining device structures were the same as in example 16. The device fabrication procedure and performance evaluation were the same as in example 15.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 2.
Comparative example 1
The difference from example 15 is that the hole transport type host material H in the electron blocking layer was used 1 The host material SF3-TRZ in the light-emitting layer was replaced with the common host material mCBP, and the electron transport material SF3-TRZ in the hole blocking layer was replaced with the electron transport material T2T. The remaining device structures, device fabrication steps, and performance evaluation methods were the same as in example 15.
The photoelectric property data of comparative example 1 is shown in table 2.
The structural formula of the material mCBP used in the organic electroluminescent device of this example is as follows:
TABLE 2 optoelectronic Performance data for the organic opto-electronic devices of examples 17-23 and comparative example 1
a Luminance of 1cd m -2 A driving voltage of time; b Current Density of 1mA cm -2 Electroluminescence of time
As can be seen from the above data, example 18 achieved higher device efficiency compared to example 17 and comparative example 1, again illustrating the strong superiority of the exciplex host. The example 17 and the example 18 almost have the same lighting voltage, and are significantly lower than the comparative example 1, and the hole transport type host material H is laterally reflected 1 The strong transmission capability, whether to introduce T2T inside the light-emitting layer, does not significantly affect the injection of carriers. However, a suitable hole transporting host material H 1 The ratio to electron transport material is still necessary to facilitate higher out-of-device quantum efficiency. Compared with the commonly used host material mCBP, the devices of examples 18 to 23 of the exciplex host respectively based on the hole transport materials H1 and H6 to H10 have higher efficiency, lower lighting voltage and better overall performance. Furthermore, examples 18 and 16 are based on the fact that the maximum external quantum efficiency of the organic electroluminescent device does not differ significantly despite being based on different electron transport materials. This result is a significant manifestation of the hole transport type host material H 1 High transmission capability and wide applicability in organic photoelectric devices.
Example 24
An organic electroluminescent device takes SF3-TRZ as a main body of a luminescent layer, and the structure of the organic electroluminescent device is as follows:
ITO(95nm)/4％F6-TCNNQ:NPB(50nm)/BCzPh(10nm)/H 1 (10nm)/15％4CzIPN:SF3-TRZ(30nm)/SF3-TRZ(10nm)/50％Liq:NBPhen(40nm)/LiF(1nm)/Al(100nm)
wherein, the transparent ITO is used as an anode, the NPB is used as a hole transport layer, the hole transport layer is doped with F-TCNNQ with the mass concentration of 4 percent, the BCzPh is used as a buffer layer, and a hole transport type main body material H is used 1 The material is an electron blocking layer, a thermal activation delayed fluorescence material 4CzIPN with the mass concentration of 15% is taken as a light-emitting object in a light-emitting layer, SF3-TRZ is taken as a light-emitting layer main body and a hole blocking layer, a blending system doped into NBPhen by 50% Liq is taken as an electron transport layer, LiF is taken as an electron injection layer, and Al is taken as a metal cathode.
The structural formula of the material BCzPh used in the organic electroluminescent device of this example is as follows:
the electroluminescent device of the present example was at 3000cd m -2 The aging decay test was performed using constant current drive under the initial brightness conditions of (1), and the device brightness decay curve with continuous operating time was subjected to fitting extrapolation using a Stretched Exponential Decay (SED) model.
The fitting formula based on the SED model in this embodiment is:
wherein, L and L 0 The real-time brightness and the initial brightness of the device under the corresponding working time of the device are respectively, tau is a decay factor, beta is an extension index, and the two are fitting factors.
The organic electroluminescent device of the present example had a current density-voltage-luminance relationship, a luminance-external quantum efficiency relationship, and a current density of 1mA cm -2 The electroluminescence spectrum and the luminance-duration operation time relationship chart at the time are shown in fig. 7, fig. 8, fig. 9 and fig. 10, respectively. The photoelectric property data are shown in table 3.
The electroluminescent device of the present example was prepared as follows:
sequentially carrying out ultrasonic cleaning on the ITO-engraved conductive glass substrate by using deionized water, tetrahydrofuran, washing liquid, deionized water and isopropanolAfter removing organic impurities, water-soluble impurities and possibly residual photoresist on the surface of the substrate, putting the substrate into an electrothermal blowing dry box to be dried for more than 3 hours to remove the residual solvent. Then taking out the dried ITO substrate, carrying out plasma treatment for 10 minutes, then conveying the ITO substrate into a vacuum evaporation chamber, and pumping until the vacuum degree is lower than 10 -4 Pa. And sequentially depositing the organic material on the ITO substrate to form a film through vacuum evaporation, wherein the doping ratio of the doping layer is regulated and controlled through a certain deposition rate ratio. And then evaporating metal aluminum to uniformly cover the organic material layer, thus completing the preparation of the device. For the device needing to test the service life, after the device is prepared, the device is packaged in a glove box isolated from water and oxygen by using epoxy resin, and a drying sheet of the Japanese Kokai company is attached to the interior of a packaging cover plate. Wherein, the epoxy resin is cured by ultraviolet irradiation in an ultraviolet curing box for 5 minutes.
The organic electroluminescent device of the present example was evaluated in the following manner:
the current density-voltage-luminance characteristic curve of the electroluminescent device was measured with a color luminance meter CS-200 (konidameter) -Keithley-2400 (gishley) programmable voltage-current source meter combination. The electroluminescence spectra of the electroluminescent devices were measured by a fiber optic spectrometer USB2000+ (ocean optics) under different current density driving conditions of Keithley-2400. Before testing the service life curve of the device, the brightness is corrected by using a CS-200-Keithley-2400 joint table, and then the device is tested by using 32-channel multi-channel service life testing equipment of Guangzhou New View optical technology Co., Ltd under the environment of room temperature of 25 ℃ and constant current driving.
Example 25
An organic electroluminescent device comprises an exciplex as the main body of luminescent layer, wherein the main body of exciplex is made of hole-transporting main material H 1 The organic electroluminescent device is blended with an electron transport type host material SF3-TRZ according to the proportion of 2:8, and the organic electroluminescent device has the following structure:
ITO(95nm)/4％F6-TCNNQ:NPB(50nm)/BCzPh(10nm)/H 1 (10nm)/15％4CzIPN:17％H 1 :68％SF3-TRZ(30nm)/SF3-TRZ(10nm)/50％Liq:NBPhen(40nm)/LiF(1nm)/Al(100nm)
in addition, the difference from example 24 is that 17% of the hole transport type host material H in the light-emitting layer 1 The exciplex composed of the polypeptide and 68% of SF3-TRZ is used as a main body. The device fabrication procedure and performance evaluation were the same as in example 24.
The method for testing the aging degradation of the electroluminescent device and the method for fitting the degradation curve of the luminance of the device with the continuous operation time are the same as those in example 24.
The organic electroluminescent device of the present example had a current density-voltage-luminance relationship graph, a luminance-external quantum efficiency relationship graph, and a current density of 1mA cm -2 The electroluminescence spectrum and the luminance-duration operation time relationship chart at the time are shown in fig. 7, fig. 8, fig. 9 and fig. 10, respectively. The photoelectric property data are shown in table 3.
TABLE 3 optoelectronic Property data of the organic opto-electronic devices of example 24 and example 25
a Luminance of 1cd m -2 A driving voltage of time; b Current Density of 1mA cm -2 Electroluminescence of time
The host in example 24 was composed of 17% of the hole transporting host material H 1 And electron transport SF 3-TRZ. From the above data, it can be seen that compared to example 24, in example 25 based on an exciplex host, the turn-on voltage is lower and the maximum external quantum efficiency of the device is higher, and the half-life of the device at 3000cd m-2 luminance is almost 1.7 times that of example 24. The result not only shows that the exciplex main body is favorable for realizing higher device efficiency and reducing the driving voltage of the device by coordinating the carrier balance, but also shows that the carrier balance realized by utilizing the exciplex greatly improves the half-life period life of the organic photoelectric device and promotes the improvement of the stability of the device.
Example 26
The difference is as compared with example 24The host material SF3-TRZ in the light-emitting layer is replaced by a hole-transporting host material H 1 The electron transport material SF3-TRZ in the hole blocking layer was changed to the electron transport material T2T. The remaining device structures, device fabrication steps, and performance evaluation methods were the same as in example 24.
The method for testing the aging degradation of the electroluminescent device and the method for fitting the degradation curve of the luminance of the device with the continuous operation time are the same as those in example 24.
The organic electroluminescent device of the present example had a current density-voltage-luminance relationship, a luminance-external quantum efficiency relationship, and a current density of 1mA cm -2 The electroluminescence spectrum and the luminance-duration operation time relationship chart at the time are shown in fig. 11, fig. 12, fig. 13 and fig. 14, respectively. Ultraviolet-visible absorption spectrum of guest material 4CzIPN and hole transport type host material H 1 The emission spectra of the film, the electron transport material T2T film, and the film with both blended in a 2:8 ratio are shown in fig. 15. The photoelectric property data are shown in table 4.
Example 27
Compared with example 24, the difference is that the host material SF3-TRZ in the light-emitting layer is replaced with the electron transporting material T2T, and the electron transporting material SF3-TRZ in the hole blocking layer is replaced with the electron transporting material T2T. The rest of the device structure, device fabrication steps, and performance evaluation methods were the same as those of example 24.
The method for testing the aging degradation of the electroluminescent device and the method for fitting the degradation curve of the luminance of the device along with the continuous working time are the same as those in the embodiment 24.
The organic electroluminescent device of the present example had a current density-voltage-luminance relationship graph, a luminance-external quantum efficiency relationship graph, and a current density of 1mA cm -2 The electroluminescence spectrum and the luminance-duration operation time relationship chart at the time are shown in fig. 11, fig. 12, fig. 13 and fig. 14, respectively. The photoelectric property data are shown in table 4.
Example 28
Compared with example 25, the difference is that the electron transport type host material SF3-TRZ in the light emitting layer is replaced with the electron transport material T2T, and the electron transport material SF3-TRZ in the hole blocking layer is replaced with the electron transport material T2T. The remaining device structure was the same as in example 25. The device fabrication procedure and performance evaluation were the same as in example 24.
The method for testing the aging degradation of the electroluminescent device and the method for fitting the degradation curve of the luminance of the device along with the continuous working time are the same as those in the embodiment 24.
The organic electroluminescent device of the present example had a current density-voltage-luminance relationship, a luminance-external quantum efficiency relationship, and a current density of 1mA cm -2 The electroluminescence spectrum and the luminance-duration operation time relationship chart at the time are shown in fig. 11, fig. 12, fig. 13 and fig. 14, respectively. The photoelectric property data are shown in table 4.
Example 29
The difference from example 25 is that the electron transport type host material SF3-TRZ in the light-emitting layer was replaced with the electron transport material T2T, the electron transport material SF3-TRZ in the hole-blocking layer was replaced with the electron transport material T2T, and the hole transport type host material H in the light-emitting layer was replaced with the hole transport type host material H 1 By substituting hole-transporting host material H 2 . The remaining device structure was the same as in example 25.
The device fabrication procedure and performance evaluation were the same as in example 24.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 4.
Example 30
The difference from example 25 is that the electron transport type host material SF3-TRZ in the light-emitting layer was replaced with the electron transport material T2T, the electron transport material SF3-TRZ in the hole-blocking layer was replaced with the electron transport material T2T, and the hole transport type host material H in the light-emitting layer was replaced with the hole transport type host material H 1 By substituting hole-transporting host material H 3 . The rest of the device structure was the same as in example 25.
The device fabrication procedure and performance evaluation were the same as in example 24.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 4.
Example 31
The difference from example 25 is that the electron transport type host material SF3-TRZ in the light-emitting layer was replaced with the electron transport material T2T, the electron transport material SF3-TRZ in the hole-blocking layer was replaced with the electron transport material T2T, and the hole transport type host material H in the light-emitting layer was replaced with the hole transport type host material H 1 By changing to hole-transporting host material H 4 . The remaining device structure was the same as in example 25.
The device fabrication procedure and performance evaluation were the same as in example 24.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 4.
Example 32
The difference from example 25 is that the electron transport type host material SF3-TRZ in the light-emitting layer was replaced with the electron transport material T2T, the electron transport material SF3-TRZ in the hole-blocking layer was replaced with the electron transport material T2T, and the hole transport type host material H in the light-emitting layer was replaced with the hole transport type host material H 1 By substituting hole-transporting host material H 5 . The rest of the device structure was the same as in example 25.
The device fabrication procedure and performance evaluation were the same as in example 24.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 4.
Example 33
The difference from example 25 is that the electron transport type host material SF3-TRZ in the light-emitting layer was replaced with the electron transport material T2T, the electron transport material SF3-TRZ in the hole-blocking layer was replaced with the electron transport material T2T, and the hole transport type host material H in the light-emitting layer was replaced with the hole transport type host material H 1 By changing to hole-transporting host material H 11 . The rest of the device structure was the same as in example 25. The device fabrication procedure and performance evaluation were the same as in example 24.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 4.
Example 34
Compared with example 25, the difference is that the electron transporting host material SF3-TR in the light emitting layerZ is replaced by an electron transport material T2T, the electron transport material SF3-TRZ in the hole blocking layer is replaced by an electron transport material T2T, and the hole transport type host material H in the light emitting layer is replaced by a hole transport type host material H 1 By changing to hole-transporting host material H 12 . The remaining device structure was the same as in example 25. The device fabrication procedure and performance evaluation were the same as in example 24.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 4.
Example 35
The difference from example 25 is that the electron transport type host material SF3-TRZ in the light emitting layer was changed to the electron transport material T2T, the electron transport material SF3-TRZ in the hole blocking layer was changed to the electron transport material T2T, and the hole transport type host material H in the light emitting layer was changed 1 By substituting hole-transporting host material H 13 . The rest of the device structure was the same as in example 25. The device fabrication procedure and performance evaluation were the same as in example 24.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 4.
Example 36
The difference from example 25 is that the electron transport type host material SF3-TRZ in the light-emitting layer was replaced with the electron transport material T2T, the electron transport material SF3-TRZ in the hole-blocking layer was replaced with the electron transport material T2T, and the hole transport type host material H in the light-emitting layer was replaced with the hole transport type host material H 1 By substituting hole-transporting host material H 14 . The remaining device structure was the same as in example 25. The device fabrication procedure and performance evaluation were the same as in example 24.
The photoelectric property data of the organic electroluminescent device of this example are shown in table 4.
Comparative example 2
The difference from example 24 is that the hole transport type host material H in the electron blocking layer was used 1 The host material SF3-TRZ in the light-emitting layer was changed to the common host material mCBP, and the electron transport material SF3-TRZ in the hole blocking layer was changed to the electron transport material T2T. The rest device structures,The device fabrication procedure and performance evaluation were the same as in example 24.
The photoelectric property data of comparative example 2 is shown in table 4.
TABLE 4 optoelectronic Performance data for the organic opto-electronic devices of examples 26-36 and comparative example 2
a Luminance of 1cd m -2 A driving voltage of time; b Current Density of 1mA cm -2 Electroluminescence of time
Examples 26 to 36 used the same device structure, the difference being that the host materials in the light emitting layer were different, with example 28 based on an exciplex host achieving the best device performance with the lowest light-on voltage, the highest external quantum efficiency, and longer device half-life. Compared with comparative example 2, the embodiment based on the exciplex host achieves lower ignition voltage, higher device efficiency and longer device lifetime under the same device structure, and exceeds the device performance obtained by the classical single host material.
The positive effect of the exciplex main body on the aspects of improving the efficiency and the service life of the device is verified again, and a hole-transporting main body material H is shown 1 Is widely applicable and indicates a hole transport type host material H 1 Has wide application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (6)
1. A hole transport host material having a general structural formula as shown in formula (I):
wherein Ar is
2. The hole transport host material according to claim 1, wherein the molecular structure of the hole transport host material is any one of the following:
3. use of a hole transporting host material according to claim 1 or 2 in the preparation of an electroluminescent device.
4. Use of a hole transporting host material according to claim 3 in the preparation of an electroluminescent device, wherein the hole transporting host material acts as a hole transporting layer.
5. The use of a hole transporting host material as claimed in claim 3 in the preparation of an electroluminescent device, wherein the hole transporting host material and the electron transporting material form an exciplex as the host material in the light-emitting layer or in the light-emitting layer.
6. The use of a hole transporting host material according to claim 5 in the preparation of an electroluminescent device, wherein the electron transporting material has a molecular structure selected from the group consisting of SF3-TRZ, T2T, TmPyPB, B3PyPB, B3PyMPM, and B4 PyMPM:
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