CN111087407A - OLED material and application thereof - Google Patents

OLED material and application thereof Download PDF

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CN111087407A
CN111087407A CN201911193208.9A CN201911193208A CN111087407A CN 111087407 A CN111087407 A CN 111087407A CN 201911193208 A CN201911193208 A CN 201911193208A CN 111087407 A CN111087407 A CN 111087407A
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oled material
compound
oled
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段陆萌
范洪涛
黄春雪
杭德余
梁现丽
李仲庆
曹占广
刘阳
班全志
李继响
罗忠林
呼建军
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Beijing Yanhua Jilian Optoelectronic Technology Co ltd
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    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
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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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Abstract

The invention relates to an OLED material which has any one structure shown in general formulas I to III. The OLED material provided by the invention takes forced-ton and ton as a parent nucleus, and the compound has a wider band gap, a high T1 energy level and a proper Highest Occupied Molecular Orbital (HOMO) energy level. The compound has high thermal stability and is not easy to decompose in the sublimation process. And has higher glass transition temperature, and can maintain the phase stability of the formed film. By introducing a group with larger steric hindrance, the luminescent material is further difficult to crystallize and quench and has good film-forming property. The OLED material provided by the invention is preferably used as a host material of a light-emitting layer in an organic electroluminescent device.

Description

OLED material and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescence display, in particular to an OLED material and application thereof.
Background
The application of the organic electroluminescent (OLED) material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. With the development of multimedia information technology, the requirements for the performance of flat panel display devices are higher and higher. The main display technologies at present are plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). The OLED has a series of advantages of self luminescence, low-voltage direct current driving, full curing, wide viewing angle, rich colors and the like, and compared with a liquid crystal display device, the OLED does not need a backlight source, has a wider viewing angle and low power consumption, has the response speed 1000 times that of the liquid crystal display device, and has a wider application prospect.
Compounds known at the present stage having condensed aromatics, for example having anthracene, pyrene or
Figure BDA0002294082130000011
However, these do not have satisfactory device properties, in particular with respect to lifetime and operating voltage. Therefore, there is still a need for further improvement of OLED materials. There is an urgent need in the market for materials with high efficiency and long life.
The Peri-xanthenoxanthene (Peri-xP1nthenoxP1nthene, PXX) is a condensed ring aromatic compound, which has 22 pi electrons in the divalent cation and its conjugated system of 22 atoms (20 carbon atoms and 2 oxygen atoms) and is very stable. The xanthenoxanthene is often used as an electron donor in charge transfer complexes and therefore has potential as a hole transport material. The merck company invents the related compounds to increase the efficiency and the service life of electronic devices, but the structure invented by the merck company is unstable, easy to quench and crystallize and poor in film forming property. At present, a fluorescent host material with high efficiency, long service life, difficult quenching and crystallization and good film forming property is urgently needed to be provided.
Disclosure of Invention
The invention aims to provide an OLED host material which is not easy to quench, crystallize and has good film-forming property, and an OLED element using the compound.
Specifically, the invention provides an OLED material, which has any one of the structures shown in general formulas I-III:
Figure BDA0002294082130000021
in the general formulas I to III, X, Y each independently represents an S atom or a Se atom, and X, Y may be the same or different.
X, Y each represents an S atom as one embodiment of the present invention.
X, Y each represents a Se atom as one embodiment of the present invention.
In the general formulas I to III, R1By substitution of H atoms at any one or two positions on the phenyl ring in which it is located, R2Substituted for any one, two or more of the phenyl rings on which they are presentH atoms in three positions, R3By substitution of H atoms in any one, two or three positions of the phenyl ring in which they are located, R4Substituted with H atoms at any one, two or three positions on the phenyl ring on which it is located.
The R is1、R2、R3、R4Each independently represents-H, -F, -Cl, -Br, -I, -n (Ar), -C (═ O) Ar, -P (═ O) Ar, -S (═ O)2Ar、-OAr、-SAr、-CN、-NO2An alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms or a sulfoalkoxy group having 1 to 40 carbon atoms.
The alkyl group having 1 to 40 carbon atoms may be a straight-chain alkyl group having 1 to 40 carbon atoms, a branched-chain alkyl group having 3 to 40 carbon atoms, or a cyclic alkyl group having 3 to 40 carbon atoms.
The alkoxy group having 1 to 40 carbon atoms may be a linear alkoxy group having 1 to 40 carbon atoms, a branched alkoxy group having 3 to 40 carbon atoms, or a cyclic alkoxy group having 3 to 40 carbon atoms.
The thioalkoxy group having 1 to 40 carbon atoms may be a linear thioalkoxy group having 1 to 40 carbon atoms, a branched thioalkoxy group having 3 to 40 carbon atoms, or a cyclic thioalkoxy group having 3 to 40 carbon atoms.
The R is1、R2、R3、R4The groups represented by each may be different, any two of them may be the same and different from the remaining two, any three of them may be the same and different from the remaining one, or four of them may be the same.
As a specific embodiment of the present invention, R is1、R2、R3、R4All represent H atoms.
In the general formulas I to III of the present invention for Ar1、Ar2The respective substitution positions are preferably selected to enhance the overall performance of the compound. Specifically, the method comprises the following steps:
in the general formula II, Ar1、Ar2Each of which is specifically substitutedThe position is preferably as shown in the general formulae II-1 to II-3.
Figure BDA0002294082130000031
In the general formula III, Ar1、Ar2The respective specific substitution positions are preferably as shown in the general formulae III-1 to III-6.
Figure BDA0002294082130000032
As a specific embodiment of the invention, the OLED material has a structure shown as a general formula II-1. As a specific embodiment of the present invention, the OLED material has a structure represented by the general formula II-1':
Figure BDA0002294082130000033
as a specific embodiment of the present invention, the OLED material has a structure represented by the general formula II-1':
Figure BDA0002294082130000041
ar of the invention1、Ar2Each independently represents a neutral aromatic group having a benzene ring and/or an aromatic heterocyclic ring or represents an H atom, and Ar1、Ar2Not H atoms at the same time.
Specifically, Ar is1、Ar2Each independently represents a neutral aromatic group containing n benzene rings and/or aromatic heterocyclic rings, and n represents an integer of 1-6; the neutral aromatic group may be selected from substituted or unsubstituted monocyclic aromatic hydrocarbons, substituted or unsubstituted polyphenolic aliphatic hydrocarbons, substituted or unsubstituted biphenyl-type aromatic hydrocarbons, substituted or unsubstituted fused ring aromatic hydrocarbons.
Preferably, Ar is1、Ar2Each independently selected from the group consisting of:
Figure BDA0002294082130000042
Figure BDA0002294082130000051
more preferably, Ar is1、Ar2Each independently selected from the group consisting of:
Figure BDA0002294082130000052
ar is1、Ar2The substituents represented by each may be the same or different.
In each of the above-mentioned substituent groups,
Figure BDA0002294082130000053
or "- - -" represents a substituted position.
As a particular embodiment of the present invention, the OLED material is selected from compounds of the following specific structures:
Figure BDA0002294082130000054
Figure BDA0002294082130000061
Figure BDA0002294082130000071
Figure BDA0002294082130000081
Figure BDA0002294082130000091
Figure BDA0002294082130000101
Figure BDA0002294082130000111
Figure BDA0002294082130000121
Figure BDA0002294082130000131
Figure BDA0002294082130000141
Figure BDA0002294082130000151
Figure BDA0002294082130000161
the invention also provides a preparation method of the OLED material. The invention also provides a preparation method of the OLED novel material.
When in formula I Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When all Ar is contained, the method for synthesizing the compound shown in the general formula I comprises the following steps: taking a compound P-I as a raw material, and carrying out a coupling reaction with Ar to obtain a compound I;
the reaction process is as follows:
Figure BDA0002294082130000162
when in formula I Ar1、Ar2When the groups are different, the method for synthesizing the compound shown in the general formula I comprises the following steps: taking a compound P-I' as a raw material, and sequentially reacting with Ar1、Ar2Carrying out coupling reaction to obtain a compound I;
the reaction process is as follows:
Figure BDA0002294082130000163
when in formula II Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When both are Ar, the method for synthesizing the compound shown in the general formula II comprises the following steps: taking a compound P-II as a raw material, and carrying out a coupling reaction with Ar to obtain a compound II;
the reaction process is as follows:
Figure BDA0002294082130000164
when in formula II Ar1、Ar2When the groups are different, the method for synthesizing the compound shown in the general formula II comprises the following steps: taking a compound P-II 'as a raw material, and reacting the compound P-II' with Ar in sequence1、Ar2Carrying out coupling reaction to obtain a compound II;
the reaction process is as follows:
Figure BDA0002294082130000171
when in formula III Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When both are Ar, the method for synthesizing the compound shown in the general formula III comprises the following steps: taking a compound P-III as a raw material, and carrying out a coupling reaction with Ar to obtain a compound III;
the reaction process is as follows:
Figure BDA0002294082130000172
when in formula III Ar1、Ar2When the groups are different, the method for synthesizing the compound shown in the general formula III comprises the following steps: taking a compound P-III 'as a raw material, and reacting the compound P-III' with Ar in sequence1、Ar2Carrying out coupling reaction to obtain a compound III;
the reaction process is as follows:
Figure BDA0002294082130000173
the above steps can be carried out by a person skilled in the art by known and conventional means, such as selecting a suitable catalyst, solvent, determining a suitable reaction temperature, time, etc.
In the above process for preparing a compound represented by any one of the general formulae I to III, when Ar is Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When both are Ar, as a preferred embodiment of the present invention, the method comprises: and (2) taking xylene as a reaction solvent, cuprous chloride as a catalyst, potassium hydroxide as an alkali, controlling the temperature to be 75-85 ℃ under the protection of nitrogen, and performing a coupling reaction on the raw materials and Ar to obtain the target compound.
In the above process for preparing a compound represented by any one of the general formulae I to III, when Ar is Ar1、Ar2When the groups are different, as a preferred embodiment of the present invention, the method comprises: firstly, dimethylbenzene is used as a reaction solvent, cuprous chloride is used as a catalyst, potassium hydroxide is used as alkali, nitrogen is used for protection, the temperature is controlled to be 75-85 ℃, and the raw material and Ar are mixed1Coupling reaction is carried out to obtain an intermediate product; and then taking toluene as a solvent, palladium acetate and tri-tert-butylphosphine as catalysts, potassium tert-butoxide as an alkali, protecting with nitrogen, controlling the temperature to be 90-120 ℃, and reacting the intermediate product and Ar2Coupling reaction is carried out to obtain the target compound.
The starting materials for the solvents, catalysts, bases, etc., used in the present invention can be synthesized by published commercial routes or methods known in the art. The invention also protects the application of the OLED material in an organic electroluminescent device. Preferably, the OLED material is used as a host material in the light emitting layer.
The invention also provides an organic electroluminescent device, wherein a luminescent layer of the organic electroluminescent device contains the OLED material. Specifically, the organic electroluminescent device protected by the invention sequentially comprises a transparent substrate, an anode layer, a hole transport layer, a light emitting layer using the OLED material as a main material, an electron transport layer, an electron injection layer and a cathode layer from bottom to top.
The OLED material provided by the invention is a novel compound which takes tonne-to-tonne as a center and has a high T1 energy level, a narrow band gap and a shallow Highest Occupied Molecular Orbital (HOMO) energy level. The perixanthenoxanthene is easily sublimable, stable in air, and does not undergo oxidative decomposition. Has high thermal stability and high glass transition temperature in air. By introducing a group with larger steric hindrance, the luminescent material is not easy to crystallize and quench and has good film-forming property.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
According to some embodiments of the present invention, the preferred solvent for preparing the organic electroluminescent device of the present invention is selected from toluene, xylene, DMF or a mixture of these solvents. The reagents are analytically pure reagents, and the intermediate is purchased from an online shopping mall or is custom-synthesized from outsourcing companies. Example 1
Figure BDA0002294082130000181
Synthesis of (Compound II-1-1)
The synthetic route is as follows:
Figure BDA0002294082130000191
synthesis of Compound II-1-1
A1 liter three-necked flask was equipped with a magnetic stirrer, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 25.62g (purity 99%, 0.21mol) of phenylboronic acid and 100ml of toluene were sequentially added. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 47.2g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 37.75g of light yellow solid with purity of 99% and yield of 81%.
Product MS (m/e): 466 of (a); elemental analysis (C)32H18S2): theoretical value C: 82.37 percent; h: 3.89 percent; s: 13.74 percent; found value C: 82.36 percent; h: 3.90 percent; s: 13.74 percent.
Example 2
Figure BDA0002294082130000192
Synthesis of (Compound II-1-12)
The synthetic route is as follows:
Figure BDA0002294082130000193
synthesis of Compound II-1-12
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 40.28g (0.38mol) of sodium carbonate, 41.58g (99% purity, 0.21mol) of 4-biphenylboronic acid and 100ml of toluene were sequentially added. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 56.6g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 57.12g of light yellow solid with purity of 99% and yield of 80%.
Product MS (m/e): 714; elemental analysis (C)44H26Se2): theoretical value C: 74.16 percent; h: 3.68 percent; se: 22.16 percent; found value C: 74.15 percent; h: 3.69 percent; se: 22.16 percent.
Example 3
Figure BDA0002294082130000201
Synthesis of (Compound II-1-21)
The synthetic route is as follows:
Figure BDA0002294082130000202
synthesis of Compound II-1-21
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 42.84g (purity 99%, 0.21mol) of 4-cyclohexylphenyl) boronic acid and 100ml of toluene were sequentially added. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 47.2g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 47.84g of light yellow solid with purity of 99% and yield of 80%.
Product MS (m/e): 630; elemental analysis (C)44H38S2): theoretical value C: 83.76 percent; h: 6.07 percent; s: 10.16 percent; found value C: 83.75 percent; h: 6.08 percent; s: 10.16 percent.
Example 4
Figure BDA0002294082130000203
Synthesis of (Compound II-1-28)
The synthetic route is as follows:
Figure BDA0002294082130000211
synthesis of Compound II-1-28
A1 liter three-necked flask was equipped with a magnetic stirrer, and after nitrogen substitution, 40.28g (0.38mol) of sodium carbonate, 47.88g (99% purity, 0.21mol) of dibenzothiophene-2-boronic acid and 100ml of toluene were sequentially added. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 48.7g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, and repeatedly boiling and washing filter cake with DMF for several times to obtain 61.76g of light yellow solid with purity of 99% and yield of 80%.
Product MS (m/e): 772; elemental analysis (C)44H22S2Se2): theoretical value C: 68.39 percent; h: 2.87 percent; s: 8.30 percent; se: 20.44 percent; found value C: 68.38 percent; h: 2.88 percent; s: 8.30 percent; se: 20.44 percent.
Example 5
Figure BDA0002294082130000212
Synthesis of (Compound II-1-29)
The synthetic route is as follows:
Figure BDA0002294082130000213
synthesis of Compound II-1-29
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 49.98g (purity 99%, 0.21mol) of 9, 9-dimethyl-9H-fluoren-3-yl) boronic acid and 100ml of toluene were added in this order. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 47.2g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing filter cake with DMF for several times, filtering to obtain 56.54g light yellow solid with purity of 99% and yield of 81%.
Product MS (m/e): 698; elemental analysis (C)50H34S2): theoretical value C: 85.92 percent; h: 4.90 percent; s: 9.18 percent; found value C: 85.91 percent; h: 4.91 percent; s: 9.18 percent.
Example 6
Figure BDA0002294082130000221
Synthesis of (Compound II-1-32)
The synthetic route is as follows:
Figure BDA0002294082130000222
synthesis of Compounds II-1-32
A1 liter three-necked flask was equipped with a magnetic stirrer, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 75.6g (purity 99%, 0.21mol) of 9, 9' -spirobifluorene-3-boronic acid and 100ml of toluene were sequentially added. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 56.6g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 80.81g of light yellow solid with purity of 99% and yield of 78%.
Product MS (m/e): 1036; elemental analysis (C)70H38Se2): theoretical value C: 81.08 percent; h: 3.69 percent; se: 15.23 percent; found value C: 81.07 percent; h: 3.70 percent; se: 15.23 percent.
Example 7
Figure BDA0002294082130000223
Synthesis of (Compound II-1-67)
The synthetic route is as follows:
Figure BDA0002294082130000231
synthesis of Compound II-1-67-1
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 20.03g (0.19mol) of sodium carbonate, 13.42g (purity 99%, 0.11mol) of phenylboronic acid and 100ml of toluene were sequentially added. After nitrogen replacement again, 0.25g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 47.2g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 22.98g of light yellow solid with purity of 99% and yield of 49%.
Synthesis of Compound II-1-67
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 20.03g (0.19mol) of sodium carbonate, 26.18g (purity 99%, 0.11mol) of (9, 9-dimethyl-9H-fluoren-3-yl) boronic acid and 100ml of toluene were sequentially added. After nitrogen replacement again, 0.25g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of 46.9g of Compound II-1-67-1 (purity 99%, 0.1mol) and 100ml of toluene was initially added dropwise, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 48.31g of light yellow solid with purity of 99% and yield of 83%.
Product MS (m/e): 582; elemental analysis (C)41H26S2): theoretical value C: 84.50 percent; h: 4.50 percent; s: 11.00; found value C: 84.49 percent; h: 4.51 percent; s: 11.00.
example 8
Figure BDA0002294082130000232
Synthesis of (Compound II-1-126)
The synthetic route is as follows:
Figure BDA0002294082130000233
synthesis of Compound II-1-126-1
A1L three-necked flask is stirred by magnetic force, and after nitrogen replacement, 20.03g (0.19mol) of sodium carbonate, 25.08g (purity 99%, 0.11mol) of benzothiophene-2-boronic acid and 100ml of toluene are added in sequence. After nitrogen replacement, 0.25g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 56.6g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing filter cake with DMF for several times, and filtering to obtain 33.45g of light yellow solid with purity of 99% and yield of 50%. Synthesis of Compound II-1-126
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 20.03g (0.19mol) of sodium carbonate, 26.18g (purity 99%, 0.11mol) of (9, 9-dimethyl-9H-fluoren-3-yl) boronic acid and 100ml of toluene were sequentially added. After nitrogen replacement again, 0.25g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of 66.9g of Compound II-1-126-1 (purity 99%, 0.1mol) and 100ml of toluene was initially added dropwise, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing filter cake with DMF for several times, filtering to obtain 61.78g of white solid with purity of 99% and yield of 79%.
Product MS (m/e): 782; elemental analysis (C)47H28SSe2): theoretical value C: 72.12 percent; h: 3.61 percent; s: 4.10 percent; se: 20.18 percent; found value C: 72.11 percent; h: 3.62 percent; s: 4.10 percent; se: 20.18 percent.
According to the technical schemes of the examples 1 to 8, the compounds shown in II-1-1 to II-1-144 can be synthesized only by simply replacing the corresponding raw materials without changing any substantial operation.
Preparing devices OLED-1-OLED-8
(1) Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (the volume ratio is 1: 1), baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3PP1, evaporating HATCN as a first hole injection layer on the anode layer film in vacuum, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a second hole injection layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 40 nm;
Figure BDA0002294082130000241
(3) evaporating and plating a layer of NPB (nitrogen-phosphorus) on the hole injection layer film to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 20 nm;
Figure BDA0002294082130000251
(4) the compound II-1-1 provided in example 1 was continuously evaporated on the hole transport layer as a host material at an evaporation rate of 0.1nm/s and BD01 as a dopant (i.e., a light-emitting material), the evaporation rate of the dye BD01 was set at a rate of 5%, and the total film thickness was 30 nm;
Figure BDA0002294082130000252
(5) continuously evaporating a layer of compound BPhen on the organic light-emitting layer to be used as an electron transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 30 nm;
Figure BDA0002294082130000253
(6) continuously evaporating a layer of LiF on the electron transport layer to be used as an electron injection layer of the device, wherein the thickness of the evaporated film is 0.5 nm;
(7) continuously evaporating a layer of Al on the electron injection layer to be used as a cathode of the device, wherein the thickness of the evaporated film is 150 nm; the OLED device provided by the invention is obtained and is marked as OLED-1.
According to the same steps as above, the compound II-1-1 in the step (4) is replaced by the compounds provided in the embodiments 2 to 8, and the devices OLED-2 to OLED-8 provided by the invention are obtained.
According to the same procedure as above, compound II-1-1 in step (4) was replaced with comparative compound 1 (structure shown below), to give comparative device OLED-9.
Figure BDA0002294082130000254
Comparative Compound 1
The results of the performance tests of the obtained devices OLED-1 to OLED-9 are shown in Table 1.
Table 1: performance test results of OLED-1 to OLED-9
Figure BDA0002294082130000261
From the above results, the current efficiency of the devices OLED-1 to OLED-8 prepared by using the OLED material provided by the invention is higher, and the working voltage is obviously lower than that of the device OLED-9 with the comparative compound 1 as the organic light-emitting main material under the condition of the same brightness.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. An OLED material, characterized by having any one of the structures shown in formulas I-III:
Figure FDA0002294082120000011
in the general formulas I to III, X, Y independently represent an S atom or a Se atom, and X, Y may be the same or different;
the R is1、R2、R3、R4Each independently represents-H, -F, -Cl, -Br, -I, -n (Ar), -C (═ O) Ar, -P (═ O) Ar, -S (═ O)2Ar、-OAr、-SAr、-CN、-NO2An alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms or a sulfoalkoxy group having 1 to 40 carbon atoms;
ar is1、Ar2Each independently represents a neutral aromatic group having a benzene ring and/or an aromatic heterocyclic ring or represents an H atom, Ar1、Ar2May be the same or different, and Ar1、Ar2Not H atoms at the same time.
2. The OLED material of claim 1, having any one of the structures of formulas II-1-II-3 and III-1-III-6:
Figure FDA0002294082120000012
Figure FDA0002294082120000021
3. OLED material according to claim 1 or 2, characterized in that R is1、R2、R3、R4All represent H atoms.
4. An OLED material as claimed in any one of claims 1 to 3 wherein X, Y each represents an S atom or X, Y each represents a Se atom.
5. The OLED material of claim 1, having a structure according to formula II-1' or formula II-1 ":
Figure FDA0002294082120000022
6. the OLED material according to any one of claims 1 to 5, wherein Ar is Ar1、Ar2Each independently represents a neutral aromatic group containing n benzene rings and/or aromatic heterocyclic rings, and n represents an integer of 1-6; the neutral aromatic group is selected from substituted or unsubstituted monocyclic aromatic hydrocarbon, substituted or unsubstituted polyphenyl aliphatic hydrocarbon, substituted or unsubstituted biphenyl aromatic hydrocarbon and substituted or unsubstituted polycyclic aromatic hydrocarbon;
preferably, Ar is1、Ar2Each independently selected from the group consisting of:
Figure FDA0002294082120000023
Figure FDA0002294082120000031
more preferably, Ar is1、Ar2Each independently selected from the group consisting of:
Figure FDA0002294082120000032
Figure FDA0002294082120000041
7. the OLED material of claim 1, wherein the compound is selected from the following specific structures:
Figure FDA0002294082120000042
Figure FDA0002294082120000051
Figure FDA0002294082120000061
Figure FDA0002294082120000071
Figure FDA0002294082120000081
Figure FDA0002294082120000091
Figure FDA0002294082120000101
Figure FDA0002294082120000111
Figure FDA0002294082120000121
Figure FDA0002294082120000131
Figure FDA0002294082120000141
8. use of the OLED material of any one of claims 1 to 7 in an organic electroluminescent device; preferably, the OLED material is used as a host material in the light emitting layer.
9. An organic electroluminescent device, characterized in that the light-emitting layer contains the OLED material according to any one of claims 1 to 7.
10. An organic electroluminescent device, comprising a transparent substrate, an anode layer, a hole transport layer, a light emitting layer using the OLED material of any one of claims 1 to 7 as a host material, an electron transport layer, an electron injection layer and a cathode layer in this order from bottom to top.
CN201911193208.9A 2019-11-28 2019-11-28 OLED material and application thereof Pending CN111087407A (en)

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US20120205628A1 (en) * 2011-02-10 2012-08-16 Xerox Corporation Semiconducting composition
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CN103087065A (en) * 2011-11-03 2013-05-08 三星显示有限公司 Ovel Heterocyclic Compound, Organic Light-emitting Device Including The Same And Flat Panel Display Device
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* Cited by examiner, † Cited by third party
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CN101490208A (en) * 2006-07-28 2009-07-22 默克专利有限公司 Novel materials for organic electroluminescent devices
JP2012012495A (en) * 2010-06-30 2012-01-19 Nippon Zeon Co Ltd Polymerizable compound, polymerizable composition, polymer and semiconductor device
US20120205628A1 (en) * 2011-02-10 2012-08-16 Xerox Corporation Semiconducting composition
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