CN108129394B - Organic electroluminescent material and preparation method and application thereof - Google Patents
Organic electroluminescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of organic electroluminescence (OLED) display, in particular to an organic electroluminescent material and application thereof in an organic electroluminescent device, and the novel OLED material provided by the invention has a structure shown in a general formula I, takes a condensed ring aromatic compound as a center, takes a benzene ring containing fluorine atoms as a bridge bond, and introduces a substituent (2-phenylimidazole) with electron transport performance into an active position of the condensed ring aromatic compound to obtain a novel OLED material with electron transport performance. The material has high electron mobility, good film stability and proper molecular energy level, and can be applied to the field of organic electroluminescence and used as an electron transport material.
Description
Technical Field
The invention relates to a novel organic material and application thereof in an organic electroluminescent device, belonging to the technical field of organic electroluminescent display.
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.
The electron transport material reported at present has the defects that the molecular weight is generally small, the glass transition temperature of the material is low, the material is easy to crystallize after repeated charging and discharging in the use process of the material, and the uniformity of a thin film is damaged, so that the service life of the material is influenced. Therefore, the stable and efficient electron transport material is developed, so that the driving voltage is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the method has important practical application value.
Disclosure of Invention
The purpose of the present invention is to provide an OLED element that can be driven at low voltage, has a long lifetime, and has high efficiency, and a compound that can provide such an OLED element.
In order to develop a compound having the above-mentioned properties and an OLED device using the compound, it has been found that the above-mentioned object can be achieved by using the compound represented by the general formula (1).
Namely, the invention provides a novel organic electroluminescent material, which has the following structural general formula:
in the above formula, Ar is selected from:
m is an integer selected from 1 to 4;
Preferably, in formula I:
ar is selected from:
and/or m is 1 or 2.
Preferably, when m is 1, the structure of formula I is selected from one of the following:
when m is 2, the structure shown in the general formula I is selected from one of the following:
as a further preferred technical solution, the organic electroluminescent material is selected from one of the following compounds:
the organic electroluminescent material has fluorine atom in the bridge bond benzene ring, so that the distance between molecules may be increased, the association between compounds may be prevented and the piling probability of molecules may be lowered. Crystallization is not easy to occur during evaporation, and the OLED device can effectively improve the OLED yield, reduce the driving voltage, improve the luminous efficiency and prolong the service life when being applied to the OLED device.
The invention also provides a preparation method of the organic electroluminescent material, which comprises two parallel schemes:
as one of the schemes, when Ar is:
the method specifically comprises the following steps:
(a) reacting a compound I-1 serving as a starting material with n-butyllithium to obtain a lithiation reagent, then performing lithiation reaction with unsaturated cyclic diketone, acidifying, and performing conventional treatment to obtain a compound I-2 under the action of sodium hypophosphite and potassium iodide;
(b) coupling reaction of the compound I-2 and 2-phenylbenzimidazole to obtain a compound I;
wherein m is an integer of 1 to 4 (in accordance with the definition in the organic electroluminescent material described above).
The above 2 steps can be realized by the ordinary means known to those skilled in the art, such as selecting suitable catalyst, solvent, determining suitable reaction temperature, time and the like.
Preferably, the preparation method comprises the following steps:
(a) taking a compound I-1 as a starting material, taking tetrahydrofuran as a solvent, reacting with n-butyl lithium at a temperature of between 90 ℃ below zero and 80 ℃ below zero, then controlling the temperature of between 90 ℃ below zero and 80 ℃ below zero, adding unsaturated cyclic diketone, and stirring for 10 +/-2 hours. Acidifying with hydrochloric acid, performing reflux reaction on acetic acid serving as a solvent and sodium hypophosphite and potassium iodide for 10 +/-2 hours after conventional treatment to obtain a compound I-2;
(b) the compound I-2 is used as an initial raw material and is subjected to a coupling reaction with 2-phenylbenzimidazole under the catalysis of piperidinecarboxylic acid and cuprous iodide to obtain the compound I.
Wherein m is an integer of 1 to 4 (in accordance with the definition in the organic electroluminescent material described above).
As a second alternative, when Ar is:
the reaction sequence is as follows:
the method comprises the following steps:
(e) taking a compound I-1 as an initial raw material, and firstly carrying out coupling reaction with 2-benzimidazole to obtain a compound I-3;
(f) the compound I-3 is subjected to lithiation reaction with n-butyl lithium, then is subjected to reaction with trimethyl borate, and is acidified to obtain a compound I-4;
(g) carrying out SUZUKI coupling reaction on the compound I-4 and dibromo polycyclic aromatic hydrocarbon to obtain a compound I;
wherein m is an integer of 1 to 4.
More preferably, the method comprises the steps of:
(e) taking a compound I-1 as an initial raw material, and carrying out catalytic coupling reaction on the compound I-1 and 2-phenylbenzimidazole through piperidinecarboxylic acid and cuprous iodide to obtain a compound I-3;
(f) taking a compound I-3 as an initial raw material and tetrahydrofuran as a solvent, firstly carrying out lithiation reaction with n-butyllithium at a temperature of-80 +/-2 ℃, then carrying out reaction with trimethyl borate, and acidifying with hydrochloric acid to obtain a compound I-4;
(g) taking toluene, ethanol and water as solvents, palladium tetratriphenylphosphine as a catalyst, sodium carbonate as alkali, and under the protection of nitrogen, carrying out SUZUKI coupling reaction on the compound I-4 and dibromo polycyclic aromatic hydrocarbon under reflux to obtain a compound I;
wherein m is an integer of 1 to 4.
As described above
Trimethyl borate, piperidinecarboxylic acid, n-butyllithium and the like can be synthesized by publicly available commercial methods or methods known per se in the literature.
The invention further provides application of the organic electroluminescent material in an organic electroluminescent device.
Preferably, the organic electroluminescent material of the present invention is used as an electron transport layer in an organic electroluminescent device.
The invention also provides an organic electroluminescent device, wherein the organic functional layer of the organic electroluminescent device comprises the compound with the general formula, and the compound is used as an electron transport material in the organic functional layer.
Preferably, the organic electroluminescent device comprises a transparent substrate, an anode layer, a hole transport layer, an organic light emitting layer, an electron transport layer, an electron injection layer and a cathode layer from bottom to top in sequence.
The material for forming the transparent substrate is a glass substrate or a flexible substrate;
the substrate may be a substrate used in a conventional organic light emitting device, for example: glass or plastic.
The anode layer is made of inorganic materials; wherein the inorganic material is at least one of Indium Tin Oxide (ITO), zinc oxide, zinc tin oxide, gold, silver or copper, preferably Indium Tin Oxide (ITO);
preferably, the glass substrate and the ITO are used as anode materials in the device manufacturing process.
The material constituting the hole transport layer is selected from various triarylamine-based materials.
The hole transport material selected for use in the fabrication of the devices of the present invention is at least one of the compounds represented by NPB and TPD:
the material constituting the organic light emitting layer is composed of a host material;
wherein the host material is any one of the following compounds:
the material for forming the electron transport layer is a compound shown in a formula I;
the material constituting the electron injection layer is selected from LiF, Li2O，MgO，Al2O3Preferably LiF.
The cathode is made of a material selected from the group consisting of lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold, and silver, preferably aluminum.
In particular, the method comprises the following steps of,
the thickness of the hole transport layer is 6-16nm, preferably 10 nm;
the thickness of the organic light-emitting layer is 15-110nm, preferably 40 nm;
the thickness of the electron transport layer is 16-60nm, preferably 30 nm;
the thickness of the electron injection layer is 1-30nm, preferably 15 nm;
the thickness of the cathode, preferably the Al layer, is 60-120nm, preferably 80 nm.
The novel OLED material provided by the invention takes a condensed-ring aromatic compound as a center, takes a benzene ring containing fluorine atoms as a bridge bond, and introduces a substituent group (2-phenylimidazole) with electron transmission performance at the active position of the condensed-ring aromatic compound to obtain the novel OLED material with the electron transmission performance. The material has high electron mobility, good film stability and proper molecular energy level, and can be applied to the field of organic electroluminescence and used as an electron transport material.
Detailed Description
The basic chemical raw materials of various phenylbenzimidazole boric acids, various bromo-anthracene, bromo-perylene, bromo-pyrene, anthraquinone, benzoanthraquinone and the like used in the invention can be conveniently purchased in domestic chemical product markets, and various phenylbenzimidazole boric acids can be synthesized by using a common organic method.
The synthesis of the compounds in the present invention can be carried out by referring to the methods of example 1, example 2 and example 3. The following describes the synthesis of some of the main compounds of the present invention.
Example 1
The synthetic route is as follows:
1) synthesis of Compound 1-1
A2000 ml three-necked flask is stirred by magnetic force, and after argon replacement, 28.2g (purity 99 percent, 0.094mol) of 1-bromo-2-fluoro-4-iodobenzene and THF500ml are added in sequence according to the above amount. n-BuLi38ml (concentration 2.5M, 0.095mol) was added dropwise at-80 ℃ followed by 8.4g of anthraquinone (purity 99%, 0.04 mol). After the addition, the temperature was controlled at-80 ℃ and the mixture was stirred for 10 hours. Adding 600m of water for hydrolysis, separating liquid, extracting an aqueous phase by using dichloromethane, combining organic layers, evaporating the solvent to dryness, adding 500ml of acetic acid, 38g of KI and 38g of sodium hypophosphite, refluxing, reacting for 10 hours, cooling, filtering, and leaching by using water to obtain 18.8g of a yellow product with the purity of 99.3 percent and the yield of 90 percent.
2) Synthesis of Compound 1
N2Under the protection of gas, 17.8g (purity 94.5%, 0.034mol) of 9, 10-bis- (3-fluoro-4-bromophenyl) anthracene, 19.79g (purity 99% 0.102mol) of 2-phenylbenzimidazole, 2.6g (purity AR0.0136mol) of copper iodide, 5.4g (purity AR0.0136mol) of piperidinecarboxylic acid and 35g (purity AR 0.254mol) of potassium carbonate were charged into a 1000mL three-necked flask. DMF 500ml, magnetic stirring, 40 hours of reflux, cool filtration, yellow solid crude product with ethanol repeatedly boiled several times, yellow solid 16.6g, purity 99.8%, yield 65%.
Product MS (m/e): 750.26, respectively;
elemental analysis (C)52H32F2N4): theoretical value C: 83.18%, H: 4.30%, F: 5.06%, N:7.46 percent; found value C: 83.16%, H: 4.28%, F: 5.18%, N: 7.38 percent.
According to the technical scheme of the example 1, the following compounds can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
Example 2:
1) synthesis of Compound 2-1
N2Under the protection of gas, 10.19g (0.034mol) of 1-bromo-2-fluoro-4-iodobenzene, 19.79g (0.102mol) of 2-phenylbenzimidazole, 2.6g (purity AR0.0136mol) of copper iodide, 5.4g (purity AR0.0136mol) of piperidinecarboxylic acid and 35g (purity AR 0.254mol) of potassium carbonate were put into a 1000mL three-necked flask. DMF (600 ml) is stirred magnetically, refluxed for 30 hours, cooled and filtered, and the crude yellow solid is boiled with ethanol for several times to obtain 9.96g of yellow solid with the purity of 99.5 percent and the yield of 80 percent.
2) Synthesis of Compound 2-2
73.2g of 2-fluoro-4- (2-phenylbenzimidazolyl) phenylborobenzene (compound 1-1, 0.2mol), 1000ml of tetrahydrofuran, nitrogen protection, liquid nitrogen cooling to-80 ℃, dropwise adding 80ml of n-butyl lithium, reacting for 3 hours at a controlled temperature after dropwise adding, dropwise adding 32g of trimethyl borate (0.30mol), reacting for 30 minutes at a controlled temperature of-80 ℃, naturally heating to-20 ℃, and dropwise adding 600ml of hydrochloric acid aqueous solution. Separating, extracting the water phase twice with 400ml × 2 ethyl acetate, combining the organic phases, and spin-drying to obtain a white solid with liquid phase purity (LC) of 99.0%, theoretical yield of 66.42g, actual yield of 59.78g, and yield of 90%;
3) synthesis of Compound 2
N2Under the protection of gas, 7.34g (purity 98%, 0.02mol) of 1, 6-dibromopyrene, 16.6g (purity 98%, 0.050mol) of 2-fluoro-4- (2-phenylbenzimidazolyl) phenylboronic acid, 0.69g (purity AR, 0.0006mol) of tetrakistriphenylphosphine palladium, 17.3g (purity AR, 0.125mol) of potassium carbonate, 400mL of toluene, 200mL of ethanol and 100mL of water were added to a 2000mL three-necked flask. Heating and refluxing the materials. After 15 hours the reaction was stopped, allowed to cool and filtered to give a yellow solid which was recrystallized twice from 20 times THF. 14.09g of a pale yellow product are obtained, with a purity of 99.90% and a yield of 91%.
Product MS (m/e): 774.26, respectively; elemental analysis (C)54H32F2N4): theoretical value C: 83.70%, H: 4.16%, F: 4.90%, N: 7.23 percent; found value C: 83.68%, H: 4.15%, F: 4.93%, N: 7.24 percent;
EXAMPLE 3 Synthesis of Compound 3
N2Under the protection of gas, 6, 12-dibromo-chrysene is added into a 1000mL three-mouth bottle
11.52g (purity 98%, 0.03mol), 24.9g (purity 98%, 0.075mol) of 2-fluoro-4- (2-phenylbenzimidazolyl) phenylboronic acid, 0.69g (purity AR, 0.0006mol) of palladium tetrakistriphenylphosphine, 25.88g (purity AR, 0.188mol) of potassium carbonate, 600ml of toluene, 100ml of ethanol and 100ml of water. Heating and refluxing the materials. After 10 hours the reaction was stopped, allowed to cool, filtered to give a yellow solid, which was recrystallized from THF and repeated twice. 19.2g of a pale yellow product are obtained, with a purity of 99.90% and a yield of 80%.
Product MS (m/e): 800.28; elemental analysis (C)56H34F2N4): theoretical value C: 83.98%, H: 4.28%, F: 4.74%, N: 7.00 percent; found value C: 83.96%, H: 4.30%, F: 4.84%, N: 6.90 percent
According to the technical schemes of the embodiment 2 and the embodiment 3, the following compounds can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
EXAMPLE 4 preparation of devices OLED-1-OLED-4
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-4Pa, evaporating a compound NPB on the anode layer film to form a hole transport layer, wherein the evaporation rate is 0.2nm/s, and the evaporation film thickness is 10 nm;
3) continuously evaporating ADN on the hole transport layer to be used as a main material and an organic light-emitting layer of the device, wherein the evaporation rate is 0.2nm/s, and the thickness of the organic light-emitting layer obtained by evaporation is 40 nm;
4) continuously evaporating a layer of the compound 1 which is prepared in the embodiment 1 and belongs to the formula I on the organic light-emitting layer to be used as an electron transport layer of a device, wherein the evaporation rate is 0.2nm/s, and the evaporation film thickness is 30 nm;
5) continuously evaporating a layer of LiF on the electron transport layer to be used as an electron injection layer of the device, wherein the evaporation rate is 0.2nm/s, and the evaporation film thickness is 15 nm;
6) continuously evaporating a layer of Al on the electron injection layer to be used as a cathode of the device, wherein the evaporation rate is 0.2nm/s, and the evaporation film thickness is 80 nm; obtaining the OLED device provided by the invention, and marking as OLED-1;
replacing the compound 1 in the step 4) with the compound 2 prepared in the example 2 according to the same procedure as above to obtain the OLED-2 provided by the invention;
replacing the compound 1 in the step 4) with the compound 3 prepared in the example 3 according to the same procedure as above to obtain the OLED-3 provided by the present invention;
replacing compound 1 in step 4) with ET1 following the same procedure as above to give a comparative device OLED-4;
ET1 (comparative Compound)
The performance test results of the obtained devices OLED-1 to OLED-4 under the same test conditions are shown in Table 1.
TABLE 1 measurement results of OLED-1 to OLED-4
From the above, the light-on voltages of the devices OLED-1 to OLED-4 prepared by using the organic electroluminescent material shown in formula I provided by the invention are lower, the current efficiency is obviously higher than that of the device OLED-4 using ET1 as an electron transport material under the condition of the same brightness, and the service life of the device is obviously prolonged.
Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims.
Claims (8)
1. An organic electroluminescent material, characterized in that: the organic electroluminescent material is selected from one of the following compounds:
2. a method for producing an organic electroluminescent material as claimed in claim 1, characterized in that: when the organic electroluminescent material is:
the method specifically comprises the following steps:
(a) taking a compound I-1 as an initial raw material, firstly reacting with n-butyllithium to obtain a lithiation reagent, then carrying out lithiation reaction with unsaturated cyclic diketone, acidifying, and obtaining a compound I-2 under the action of sodium hypophosphite and potassium iodide, wherein the unsaturated cyclic diketone is 9, 10-anthraquinone;
(b) the compound I-2 and 2-phenyl benzimidazole are coupled to react to obtain a compound
When the organic electroluminescent material is:
the method comprises the following steps:
(e) taking a compound I-1 as an initial raw material, and firstly carrying out coupling reaction with 2-phenylbenzimidazole to obtain a compound I-3;
(f) the compound I-3 is subjected to lithiation reaction with n-butyl lithium, then is subjected to reaction with trimethyl borate, and is acidified to obtain a compound I-4;
(g) carrying out SUZUKI coupling reaction on the compound I-4 and dibromo polycyclic aromatic hydrocarbon to obtain a compound
Wherein the dibromo polycyclic aromatic hydrocarbon is
3. Use of the organic electroluminescent material according to claim 1 in an organic electroluminescent device.
4. Use according to claim 3, characterized in that: the organic electroluminescent material is used as an electron transport layer in the organic electroluminescent device.
5. An organic electroluminescent device, characterized in that: comprising an electron transport layer made of the organic electroluminescent material as claimed in claim 1.
6. The organic electroluminescent device according to claim 5, wherein: the organic electroluminescent device consists of a transparent substrate, an anode layer, a hole transport layer, an organic light emitting layer, an electron transport layer, an electron injection layer and a cathode layer from bottom to top in sequence.
7. The organic electroluminescent device according to claim 6, wherein: the transparent substrate is made of a glass substrate or a flexible substrate;
and/or; the anode layer is made of at least one material selected from indium tin oxide, zinc oxide, tin zinc oxide, gold, silver and copper;
and/or; the material constituting the hole transport layer is at least one of compounds represented by NPB and TPD:
and/or; the host material constituting the organic light-emitting layer is any one of the following compounds:
and/or; the material constituting the electron injection layer is selected from LiF, Li2O, MgO or Al2O3One of (1);
and/or; the cathode layer is made of a material selected from one of lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold, and silver.
8. The organic electroluminescent device according to claim 6 or 7, characterized in that: the thickness of the hole transport layer is 6-16 nm; the thickness of the organic light-emitting layer is 15-110 nm; the thickness of the electron transmission layer is 16-60 nm; the thickness of the electron injection layer is 1-30 nm; the thickness of the cathode layer is 60-120 nm.
Priority Applications (1)
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| CN101875637A (en) * | 2009-11-13 | 2010-11-03 | 昆山维信诺显示技术有限公司 | Organic material and application thereof in organic electroluminescence devices |
| CN102082232A (en) * | 2010-09-16 | 2011-06-01 | 昆山维信诺显示技术有限公司 | Blue light organic electroluminescence device |
| CN102082231A (en) * | 2010-09-16 | 2011-06-01 | 昆山维信诺显示技术有限公司 | Green organic electroluminescent device |
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| CN101875637A (en) * | 2009-11-13 | 2010-11-03 | 昆山维信诺显示技术有限公司 | Organic material and application thereof in organic electroluminescence devices |
| CN102082232A (en) * | 2010-09-16 | 2011-06-01 | 昆山维信诺显示技术有限公司 | Blue light organic electroluminescence device |
| CN102082231A (en) * | 2010-09-16 | 2011-06-01 | 昆山维信诺显示技术有限公司 | Green organic electroluminescent device |
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