CN108948030B - Azafluorene spiroanthracene heterocyclic compound and application thereof in organic electroluminescent element - Google Patents
Azafluorene spiroanthracene heterocyclic compound and application thereof in organic electroluminescent element Download PDFInfo
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Abstract
The invention relates to a azafluorene spiroanthracene heterocyclic compound and application thereof in an organic electroluminescent element, wherein the azafluorene spiroanthracene heterocyclic compound is shown in a general formula (1), and a matrix of the azafluorene spiroanthracene heterocyclic compound is connected with groups such as furan, carbazole, thiophene, fluorene, heteroaryl amino, acridine, phenazine and the like.
Description
Technical Field
The invention relates to the field of organic electroluminescent functional materials, in particular to a azafluorene spiroanthracene heterocyclic compound and application thereof in an organic electroluminescent element.
Background
The luminous mechanism of an organic electroluminescent oled (organic Light Emission diodes) display lighting element, which is a self-luminous electronic element, is a novel photoelectric information technology that converts electric energy directly into Light energy by means of an organic semiconductor functional material under the action of a direct current electric field. The light emission color can be red, green, blue, yellow alone or combined white. The biggest characteristics of the OLED light-emitting display technology are ultrathin, ultra-light weight, surface light-emitting and flexible display, and the OLED light-emitting display technology can be used for manufacturing monochromatic or panchromatic displays, can be used as a novel light source technology, and can also be used for manufacturing lighting products or a novel backlight source technology for manufacturing liquid crystal displays.
Organic electroluminescent elements (organic EL elements) can be classified into two types, i.e., fluorescent type and phosphorescent type, according to the principle of light emission. When a voltage is applied to the organic EL element, holes from the anode and electrons from the cathode are injected, and they are recombined in the light-emitting layer to form excitons. According to the electron spin statistic method, singlet excitons and triplet excitons are generated in a ratio of 25% to 75%. The fluorescent type uses singlet excitons to emit light, and thus its internal quantum efficiency can only reach 25%. A Thermally Active Delayed Fluorescence (TADF) material is a third generation organic light emitting material developed after organic fluorescent materials and organic phosphorescent materials. The material generally has smaller singlet-triplet energy level difference (delta Est), triplet excitons can be converted into singlet excitons through reverse gap crossing to emit light, the singlet excitons and the triplet excitons formed under electric excitation can be fully utilized, the internal quantum efficiency of the device can reach 100 percent, meanwhile, the material has controllable structure, stable property and low price, does not need precious metal, and has wide application prospect in the field of OLEDs.
In order to prepare a high-performance OLED light-emitting device, a high-performance OLED functional material needs to be selected and used, and for OLED functional materials with different functions, the basic requirements needed to be met are as follows:
1. the material has good thermal stability, namely, the material can not be decomposed in the long-time evaporation process, and meanwhile, the material is required to have good process reproducibility;
2. the OLED light-emitting device manufactured by matching with the OLED functional material has good performance, namely, better efficiency, longer service life and lower voltage are required. This requires materials with appropriate highest molecular occupied orbitals, lowest molecular unoccupied orbitals (HOMO, LUMO), and appropriate triplet energies.
In recent years, although the development of OLED functional materials has made some breakthrough, as lighting or display applications, there is a need to develop and innovate materials with better performance, especially organic functional materials with longer lifetime and better performance that can be applied to phosphorescent OLED systems and TADF systems.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an azafluorene spiroanthracene heterocyclic compound capable of improving the use efficiency and the service life of an organic electroluminescent device and application thereof in an organic electroluminescent element.
The technical solution of the invention is as follows: an azafluorene spiroanthracene heterocyclic compound represented by the following general formula (1):
in the formula (1), the reaction mixture is,
x is oxygen atom, sulfur atom, sulfuryl, boron atom; wherein A, B, C, D are the same or different,
A. b, C, D is represented by the following general formula (2), (3) or (4),
in the formula (2), L is a divalent to hexavalent aryl or heteroaryl connecting group, and n is an integer of 1-5;
Ar1、Ar2identical or different, phenyl, biphenyl, naphthyl, carbazolyl, furyl, thienyl, fluorenyl, acridine, thiophene oxazine, and optionally substituted C6To C30One of aromatic heterocyclic groups, wherein the substituent group comprises phenyl, carbazolyl and arylamine;
in the formula (3), L is a divalent to hexavalent aryl or heteroaryl connecting group, and n is an integer of 1-5; y is oxygen atom or sulfur atom、NR3Or CR1R2Wherein R is1、R2Respectively is one of hydrogen atom, methyl, ethyl, propyl, tertiary butyl and phenyl, R3Is hydrogen atom, phenyl, biphenyl, naphthyl, carbazolyl, furyl, thienyl, fluorenyl, acridine, thiophene oxazine or C which is substituted or unsubstituted at any position6To C30One of aryl, wherein the substituent is benzene, biphenyl, dibenzofuran, carbazole, 9-dimethylfluorene and dibenzothiophene;
w in the formula (4) is oxygen atom, sulfur atom, NR4、CR5R6Wherein R is5、R6Respectively is one of hydrogen atom, methyl, ethyl, propyl, tertiary butyl and phenyl, R4Is hydrogen atom, phenyl, biphenyl, naphthyl, carbazolyl, furyl, thienyl, fluorenyl, acridine, thiophene oxazine or C which is substituted or unsubstituted at any position6To C30One of aromatic heterocyclic groups, wherein the substituent is dibenzofuran, carbazole, 9-dimethylfluorene or dibenzothiophene;
l in the general formulas (2) and (3) is a 5-membered heterocyclic aryl group with 6-30 ring-forming carbon atoms substituted or unsubstituted at any position, a second heterocyclic group with 5-30 ring-forming carbon atoms substituted or unsubstituted at any position, or a combination of 2-3 phenyl groups, naphthyl groups and 2-3 pyridine, pyrimidine, carbazole and furan heterocyclic groups, and the substituent group comprises phenyl, carbazole and arylamine.
L in the general formulas (2) and (3) is phenyl, biphenyl, carbazole and fluorene.
In the general formulas (2) and (3), when n is 1, L is a divalent connecting group; and when n is 2-5, L is a trivalent-hexavalent connecting group.
The preferred structure of formula (2) is one of the following:
the preferred structure of formula (3) is one of the following:
the preferred structure of formula (4) is one of the following:
the azafluorene spiroanthracene heterocyclic compound is applied to an organic electroluminescent element.
An organic electroluminescent element comprising:
an anode (1) and a cathode (10) which face each other;
at least one organic layer located between the anode (1) and the cathode (10); the organic layer sequentially comprises a transparent conductive film (2), a hole injection layer (3), a first hole transport layer (4), a second hole transport layer (5), a light-emitting layer (6), a hole blocking layer (7), an electron transport layer (8) and an electron injection layer (9);
wherein the light-emitting layer (6) contains a material made of the azafluorene spiroanthracene heterocyclic compound.
The hole blocking layer (7) and the electron transport layer (8) respectively comprise materials made of the azafluorene spiroanthracene heterocyclic compound.
The organic electroluminescent element is applied to an organic electroluminescent display device.
The invention has the beneficial effects that: the azafluorene spiroanthracene heterocyclic compound provided by the invention has a structure similar to that of a fluorene spiroxanthene derivative, a fluorene spiroazaanthracene derivative, a fluorene spirothianthrene derivative and a fluorene spiroboranthrene derivative, can improve carrier transport property, improve triplet state energy of materials, optimize HOMO/LUMO value of the materials, and realize high brightness, low voltage, high efficiency and long service life of an organic EL element.
Drawings
Fig. 1 is a schematic structural diagram of an organic electroluminescent device according to the present invention.
Description of reference numerals:
1-a substrate; 2-a transparent conductive film; 3-a hole injection layer;
4-a first hole transport layer; 5-a second hole optical layer; 6-a light emitting layer;
7-a hole blocking layer; 8-an electron transport layer; 9-electron injection
10-cathode.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
An azafluorene spiroanthracene heterocyclic compound represented by the following general formula (1):
in the formula (1), the reaction mixture is,
x is oxygen atom, sulfur atom, sulfuryl, boron atom; wherein A, B, C, D are the same or different,
A. b, C, D is represented by the following general formula (2), (3) or (4),
in the formula (2), L is a divalent to hexavalent aryl or heteroaryl connecting group, and n is an integer of 1-5;
Ar1、Ar2identical or different, phenyl, biphenyl, naphthyl, carbazolyl, furyl, thienyl, fluorenyl, acridine, thiophene oxazine, and optionally substituted C6To C30One of aromatic heterocyclic groups, wherein the substituent group comprises phenyl, carbazolyl and arylamine;
in the formula (3), L is a divalent to hexavalent aryl or heteroaryl connecting group, and n is an integer of 1-5; y is oxygen atom, sulfur atom, NR3Or CR1R2Wherein R is1、R2Respectively is one of hydrogen atom, methyl, ethyl, propyl, tertiary butyl and phenyl, R3Is hydrogen atom, phenyl, biphenyl, naphthyl, carbazolyl, furyl, thienyl, fluorenyl, acridine, thiophene oxazine or C which is substituted or unsubstituted at any position6To C30One of aryl, wherein the substituent is benzene, biphenyl, anthracene, naphthalene, dibenzofuran, carbazole, 9-dimethylfluorene and dibenzothiophene;
w in the formula (4) is oxygen atom, sulfur atom, NR4、CR5R6Wherein R is1、R2Respectively is one of hydrogen atom, methyl, ethyl, propyl, tertiary butyl and phenyl, R3Is hydrogen atom, phenyl, biphenyl, naphthyl, carbazolyl, furyl, thienyl, fluorenyl, acridine, thiophene oxazine or C which is substituted or unsubstituted at any position6To C30One of aromatic heterocyclic groups, wherein the substituent is benzene, biphenyl, dibenzofuran, carbazole, 9-dimethylfluorene or dibenzothiophene;
specific examples of the group connected to the group A, B, C, D by a single bond in the general formula (1) are shown below:
[ solution 5]
Specific examples of the group represented by the general formula (2) are shown below:
[ solution 6]
Specific examples of the group represented by the general formula (3) are shown below:
[ solution 7]
Specific examples of the compound represented by the general formula (1) of the present invention are as follows:
[ solution 8]
[ solution 9]
[ solution 10]
[ solution 11]
[ solution 12]
[ solution 13]
The invention provides an organic electroluminescent element, which contains an azafluorene spiroanthracene heterocyclic compound shown in a general formula (1), and the organic electroluminescent element can be a phosphorescent device, a fluorescent device or a device containing a Thermal Activity Delayed Fluorescence (TADF) material under the condition of no specific limitation.
Fig. 1 shows an example of an organic electroluminescent device. An organic electroluminescent element according to one embodiment includes an anode 1, an organic layer, and a cathode 10 in this order, the organic layer including a transparent conductive film 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, and an electron injection layer 9 in this order; the anode 1 may be formed of Indium Tin Oxide (ITO) having a high work function to facilitate hole injection, and the cathode 10 may be a metal electrode of aluminum, magnesium, silver, or the like having a low work function. The organic layer at least comprises one layer of azafluorene spiroanthracene heterocyclic compound, the azafluorene spiroanthracene heterocyclic compound can be used as a main body of the light-emitting layer 6, the azafluorene spiroanthracene heterocyclic compound can be used alone when the compound is used as the main body of the light-emitting layer 6, or the azafluorene spiroanthracene heterocyclic compound can be used together with other organic materials such as 4,4' - (9-Carbazolyl) Biphenyl (CBP) to form a mixed main body. When the material is used as a main body, the material can be matched with a fluorescent material, a phosphorescent material or a TADF material. The azafluorene spiroanthracene heterocyclic compound may also be used as the second hole transport layer 5. The organic light-emitting element also comprises auxiliary functional layers such as a hole injection layer 3, a first hole transport layer 4, an electron transport layer 8, an electron injection layer 9, a transparent conductive film 2 and the like so as to improve the photoelectric property of the device. The specific application effect of the synthesized organic electroluminescent functional material of the present invention in the device is explained in detail by the device example and the comparative example 1.
Example 1:
adding 130 g of compound, 12.6g of phenol, 300ml of Dimethylformamide (DMF) and 10ml of pyridine into a 500ml three-necked bottle in sequence, introducing nitrogen for 15min, stirring to completely dissolve the raw materials, adding 26.4g of potassium carbonate and 1.2g of cuprous iodide, stirring for 5min, heating to 100 ℃, stirring for reacting for 8h, sampling, monitoring, and cooling to room temperature after the raw materials are completely reacted. Adding 2M hydrochloric acid solution to adjust the pH value to acidity, separating out a large amount of white solid, extracting by ethyl acetate for 3X 500ml, combining organic phases, washing by water to neutrality, drying by anhydrous magnesium sulfate, then spin-drying the solvent, drying the obtained white solid by air for 32.8g, obtaining the yield of 88.2 percent, and directly using the white solid in the next reaction without further treatment.
1H NMR(400MHz,CDC13)7.98(d，J＝8.4,1H)，7.36(dd，J＝8.4， 1H)，7.30(s，1H)，7.22(d，J＝7.2，2H)，6.98(t，J＝7.2，1H)，6.92(d， J＝7.2，2H)；
In a 500ml three-necked flask, 230 g of compound was charged, then 300ml of concentrated sulfuric acid was added, and the mixture was stirred to 100 ℃ and reacted for 2 hours. After the temperature is reduced to room temperature, the reaction liquid is poured into ice water, dichloromethane is added for extraction, the organic phase is adjusted to be neutral by 1N sodium hydroxide solution, the water is washed twice and dried by anhydrous sodium sulfate, drying agents are removed by filtration, the filtrate is concentrated and then is purified by a column, and the target product compound 3 is 15.1g of white solid, and the yield is 53.6%.
1H NMR(400MHz,CDC13)8.33(dd，J＝8.4,1H)，8.21(d，J＝8.0， 1H)，7.79-7.70(m，2H)，7.54-7.47(m，2H)，7.41(t，J＝7.2，1H)；
Adding 2g of magnesium chips, iodine and a small amount of Tetrahydrofuran (THF) into a 500ml three-necked flask, dropwise adding a small amount of 2- (2-bromophenyl) pyridine, continuously and slowly dropwise adding 200ml of Tetrahydrofuran (THF) solution of 2- (2-bromophenyl) pyridine (19g) after initiating reaction, dropwise adding 100ml of THF solution of 15g compound 3 after the magnesium chips disappear through reflux reaction, continuously carrying out reflux reaction for 8 hours, cooling to room temperature, adding 2N hydrochloric acid for quenching reaction, evaporating the solvent under reduced pressure, adding 300ml of acetic acid into the obtained solid, and heating to reflux reaction for 2 hours. The temperature is reduced to room temperature, the solvent is removed by filtration, the obtained white solid is dissolved in 100THF, then methanol with the same amount is slowly added, and the white solid product is stirred and separated out, wherein the yield is 16.3g, and 72.6%.
1H NMR(400MHz,CDC13)8.54(d，J＝8.0,1H)，7.87(6，J＝7.2， 1H)，7.41(d，J＝7.6，1H)，7.14-7.16(m，3H)，6.86-7.04(m，7H)，6.80(d， J＝7.2，1H)；
Adding 16g of compound 4 into a 500ml three-neck bottle, then sequentially adding 7.7g of carbazole, 10.7g of potassium carbonate, 0.3g of 1, 10-phenanthroline, adding 300ml of toluene, introducing nitrogen, adding 0.3g of cuprous bromide under the protection of nitrogen, heating and refluxing for 8h, stopping stirring after TLC monitors that the raw materials are completely reacted, and cooling to room temperature. Washing the reaction system with water to be neutral, drying the organic phase for 2h by using anhydrous sodium sulfate, concentrating, passing the crude product through a silica gel column, and recrystallizing to obtain the target product compound 1 which is 17.3g of white solid with the yield of 89.7%.
1H NMR(400MHz,CDC13)8.55(d，J＝8.4,1H)，7.87(d，J＝7.4， 1H)，7.55(d，J＝7.4，2H)，7.40-7.42(m，3H)，7.14-7.16(m，3H)，7.08(d， J＝7.4，2H)，6.98-7.03(m，5H)，6.84-6.89(m，5H)；
Example 2:
in a 500ml three-necked flask were added 20g of compound 5, 150ml of THF in this order, and the mixture was cooled to 0 ℃ under nitrogen. 125ml of a 1.0M in THF solution of phenylmagnesium bromide were slowly added dropwise. Heating to room temperature, continuing to react for 2h, sampling and detecting, stopping stirring when the raw materials completely react, and adding an ammonium chloride aqueous solution to quench the reaction. Standing, separating, extracting water phase with dichloromethane, mixing organic phases, washing with saturated salt water, drying with anhydrous sodium sulfate, and purifying with column to obtain yellow solid 17.6g with yield of 63.7%
1H NMR(400MHz,CDC13)9.13(d，J＝8.4,1H)，8.58(d，J＝8.4， 1H)，8.04(t，J＝8.4，1H)，7.81(d，J＝7.6，2H)，7.54(t，J＝7.6，1H)， 7.45(t，J＝7.6，2H)；
16g of compound 6, 20.3g of potassium carbonate and 2.2g of pivalic acid are added into a 500ml three-neck flask, then 300ml of toluene is added, the air in the reaction flask is replaced by nitrogen, 0.8g of palladium acetate and 2.2g of tri-tert-butylphosphine are added under the protection of nitrogen, the temperature is raised to reflux reaction for 8 hours, then sampling is carried out, detection is carried out, and the reaction is stopped when the raw materials are completely reacted. The mixture is cooled to room temperature, washed to be neutral by water, the organic phase is dried for 2 hours by anhydrous sodium sulfate, the drying agent is removed by filtration, and the target product compound 7 is obtained by concentration and then column chromatography, wherein the yield is 78.3 percent, and the target product compound 7 is 10.4g of yellow solid.
1H NMR(400MHz,CDC13)8.90(d，J＝8.4,1H)，8.18(d，J＝8.0， 1H)，8.01(d，J＝8.4，1H)，7.90(d，J＝8.0，1H)，7.63(t，J＝8.0，1H)， 7.47(t，J＝8.0，1H)，7.35(t，J＝8.0，1H)；
10g of compound 7, 38.2g of 3-bromophenol and 21.2g of methanesulfonic acid were put into a 250ml three-necked flask, 150ml of xylene was then added, the air in the flask was replaced with nitrogen, the temperature was raised to 140 ℃ and the reaction was stopped after 8 hours of reaction by sampling and detecting when the reaction of the starting materials was completed. After cooling to room temperature, the reaction mixture was poured into ice water, extracted with dichloromethane (2X 100ml), the organic phase was washed with water to neutrality, dried over anhydrous sodium sulfate for 2 hours, filtered to remove the drying agent, and the filtrate was concentrated and then passed through a column to obtain the desired product, compound 8, 19.7g as a yellow solid in a yield of 72.9%.
1H NMR(400MHz,CDC13)8.54(d，J＝8.4,1H)，7.87(d，J＝7.6， 1H)，7.41(d，J＝8.0，1H)，7.14-7.16(m，3H)，6.98-7.02(m，4H)， 6.88-6.92(m，3H)；
Adding 8g of compound 8, 8.2g of carbazole, 6.7g of potassium carbonate, 0.2g of 1, 10 phenanthroline and 100ml of toluene into a 250ml three-neck bottle, introducing nitrogen, then adding 0.2g of cuprous bromide, heating a reaction system to reflux and stir for reaction for 8 hours, monitoring by TLC (thin layer chromatography) that the raw materials are completely reacted, cooling to room temperature, washing with water to be neutral, drying an organic phase for 2 hours by using anhydrous sodium sulfate, filtering, passing a concentrated solvent through a silica gel column, recrystallizing toluene to obtain 8.9g of a target product compound 2 which is a white solid, wherein the yield is 82.6%.
1H NMR(400MHz,CDC13)8.54(d，J＝8.4,1H)，7.87(d，J＝7.6， 1H)，7.55(d，J＝7.6，4H)，7.40(d，J＝7.6，5H)，7.14-7.16(m，3H)， 7.08(d，J＝7.6，4H)，7.00(t，J＝7.6，4H)，6.86-6.92(m，7H)；
Example 3:
adding 8g of compound 8, 8.2g of diphenylamine, 6.7g of potassium carbonate, 0.2g of 1, 10-phenanthroline and 100ml of toluene into a 250ml three-neck bottle, introducing nitrogen, then adding 0.2g of cuprous bromide, heating a reaction system to reflux and stir for reaction for 8 hours, monitoring by TLC (thin layer chromatography), cooling the reaction system to room temperature after the raw materials are completely reacted, washing with water to be neutral, drying an organic phase for 2 hours by using anhydrous sodium sulfate, filtering, passing a concentrated solvent through a silica gel column, recrystallizing toluene to obtain 9.5g of a target product compound 3 which is a white solid, wherein the yield is 87.7%.
1H NMR(400MHz,CDC13)8.54(d，J＝8.4,1H)，7.87(d，J＝7.6， 1H)，7.41(d，J＝7.6，1H)，7.14-7.16(m，3H)，7.01(t，J＝7.6，8H)， 6.89(t，J＝8.4，1H)，6.77(m，2H)，6.62(t，J＝7.6，4H)，6.46(t，J＝7.6， 8H)，6.06(dd，J＝7.6，2H)，6.00(s，J＝7.6，2H)；
The effect of the OLED material of the present invention in the device application is detailed below by the device performance of device examples 4-8 and comparative examples 1 and 2. The manufacturing processes of the embodiments 4 to 8 are completely the same as those of the comparative examples 1 and 2, the same glass substrate and electrode material are adopted, the film thickness of the electrode material is kept consistent, and different embodiments 4 to 6 and 1 change the main body material of the light emitting layer in the device; examples 7 to 8 and comparative example 2 were carried out by changing the second hole transport layer (HT2) and the host material of the light emitting layer of the device, and the results of the performance test of each example are shown in table 4.
Example 4
An organic electroluminescent device, the device preparation steps comprising:
1) cleaning an ITO anode 1 on a transparent glass substrate, respectively ultrasonically cleaning the ITO anode 1 for 20 minutes by using deionized water, acetone and ethanol, and then carrying out Plasma treatment for 5 minutes in an oxygen atmosphere;
2) evaporating a hole injection layer material HAT-CN on the ITO anode layer in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 5nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3;
3) evaporating a hole transport material NPB on the hole injection layer in a vacuum evaporation mode, wherein the thickness of the hole transport material NPB is 60nm, and the hole transport layer is used as a first hole transport layer 4;
4) evaporating a hole transport material TAPC (titanium polycarbonate) on the first hole transport layer NPB in a vacuum evaporation mode, wherein the thickness of the hole transport material TAPC is 15nm, and the layer serves as a second hole transport layer 5;
5) on the second hole transport layer, a light emitting layer 6 was deposited by vacuum deposition, using the compound 1 of the present invention as a host material, Ir (ppy)3As a doping material, the doping amount ratio is 10%, and the thickness is 30 nm;
6) evaporating a hole blocking material TPBI on the light-emitting layer in a vacuum evaporation mode, wherein the thickness of the hole blocking material TPBI is 10nm, and the layer is used as a hole blocking layer 7;
7) evaporating an electron transport material ET-1 on the hole blocking layer in a vacuum evaporation mode, wherein the thickness of the electron transport material ET-1 is 35nm, and the electron transport material ET-1 serves as an electron transport layer 8;
8) evaporating an electron injection material Liq with the thickness of 2nm on the electron transport layer in a vacuum evaporation mode, wherein the electron injection material Liq is used as an electron injection layer 9;
9) on the electron injection layer, a cathode Al was deposited by vacuum deposition to a thickness of 120nm, and this layer was used as a conductive electrode of the cathode 10.
The structural formula of the basic material is as follows:
example 5
The same as example 4, except that: compound 2 was used as the host material in place of compound 1.
Example 6
The same as example 4, except that: compound 3 was used as the host material in place of compound 1.
Example 7
The same as example 5, except that: compound 2 was used as the second hole transport material instead of TAPC.
Example 8
The same as example 6, except that: compound 3 was used as the second hole transport material instead of TAPC.
Comparative example 1
The same as example 5, except that: CBP was used as host material instead of compound 1.
Comparative example 2
Same as comparative example 1 except that: CBP as the host material instead of compound 1, compound 3 as the second hole transport material.
Glass transition temperatures (T) of the compounds of Table 1g)
As can be seen from Table 1, the compound material of the present invention has a high glass transition temperature (T)g) The light-emitting device has relatively stable deformation in a higher temperature range, namely has higher thermal stability, and can obviously improve the light-emitting stability of the light-emitting device when being applied to the light-emitting device. As can be seen from tables 1 and 4, the material properties of compound 2 are optimal, and the glass transition temperature and lifetime characteristics are high.
The azafluorene spiroanthracene heterocyclic compound is used in a luminescent device and has higher TgTemperature and triplet energy (T)1) Suitable HOMO and LUMO energy levels can be used as the second hole transporting material and also as the material of the light emitting layer. Respectively carrying out T on the azafluorene spiroanthracene heterocyclic compound and the existing material1Energy level and HOMO, LUMO energy level measurementsThe results of the tests are shown in Table 2.
TABLE 2
Note: the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) are measured by cyclic voltammetry, T1Measured by an F4600 fluorescence spectrum analyzer, the measurement environment was the atmospheric environment.
As can be seen from Table 2, the azafluorene spiroanthracene heterocyclic compound provided by the invention has higher triplet energy and more appropriate HOMO/LUMO, and is beneficial to carrier transport and energy transfer in an OLED device. Therefore, the organic material containing the azafluorene spiroanthracene heterocyclic compound can effectively improve the luminous efficiency and prolong the service life of the device after being applied to different functional layers of an OLED device.
According to the azafluorene spiroanthracene heterocyclic compound provided by the invention, X in an anthracene heterocyclic ring is an oxygen atom, a sulfur atom, a sulfone group or a boron atom, the electron-withdrawing property of a ligand can be increased after nitrogen hybridization on fluorene, and when X is a sulfone group or a boron atom, a core structure has a strong electron-withdrawing property, and a bipolar material can be obtained by substituting electron-rich groups such as carbazole, amine derivatives and the like. The application of the organic electroluminescent material to a luminescent layer main body material or a second hole transport material can effectively improve the luminous efficiency of a luminescent element and realize low voltage and long service life greatly. As can be seen from Table 4, when the compound provided by the invention is used as a main material of a light-emitting layer and a second hole transport material (HT2) and applied to an OLED (organic light emitting diode) light-emitting device, the chromaticity is stable, compared with comparative example 1, the light-emitting efficiency and the service life are remarkably improved, the light-emitting efficiency is improved by more than 10%, and the service life is improved by about 1-2 times; compared with comparative example 1, the luminous efficiency and the service life of the second hole transport layer are improved after the compound of the invention is added.
Meanwhile, the spiral structure has stronger rigidity, and can improve the glass transition temperature (T) of the compoundg) T is performed on a material containing the compound of examples 1 to 3gThe test experiments were tested and the results are shown in table 1.
TABLE 3 List of different devices of inventive examples 5 to 8, comparative example 1 and comparative example 2
| Examples | A first hole transport layer | Second hole transport layer | Luminescent | HB | ET | |
| 4 | NPB | TAPC | Compound 1: ir (ppy)3 | TPBI | ET-1 | |
| 5 | NPB | TAPC | Compound 2: ir (ppy)3 | TPBI | ET-1 | |
| 6 | NPB | TAPC | Compound 3: ir (ppy)3 | TPBI | ET-1 | |
| 7 | | Compound | 2 | Compound 2: ir (ppy)3 | TPBI | ET-1 |
| 8 | NPB | Compound 3 | Compound 3 | TPBI | ET-1 | |
| Comparative example 1 | NPB | TAPC | CBP：Ir(ppy)3 | TPBI | ET-1 | |
| Comparative example 2 | | Compound | 2 | CBP：Ir(ppy)3 | TPBI | ET-1 |
Compared with the device in embodiment 5, the device in embodiments 4 to 8, comparative example 1 and comparative example 2 of the present invention has the same manufacturing process, and uses the same substrate material and electrode material, and the thickness of the electrode material is also the same, except that the device in embodiments 4 to 8, comparative example 1 and comparative example 2 changes the host material or the second hole transport material of the light emitting layer of the device. In the above-mentioned OLED light-emitting device, the cathode and the anode are connected by a known driving circuit, and the voltage-efficiency-current density relationship of the OLED device is tested by a standard method; the service life of the device is tested by a constant current method under the condition that the constant current density is 10mA/cm2The time for the test brightness to decay to 95% of the initial brightness is the device LT95And (4) service life. The test results are shown in table 4.
Table 4 table of performance of different device embodiments
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. An azafluorene spiroanthracene heterocyclic compound characterized by being represented by the following structural formula:
[ solution 8]
[ solution 9]
[ solution 10]
[ solution 11]
[ solution 12]
[ solution 13]
2. Use of the azafluorene spiroanthracene heterocyclic compound according to claim 1 in an organic electroluminescent device.
3. An organic electroluminescent element, comprising:
an anode (1) and a cathode (10) which face each other;
at least one organic layer located between the anode (1) and the cathode (10); the organic layer sequentially comprises a transparent conductive film (2), a hole injection layer (3), a first hole transport layer (4), a second hole transport layer (5), a light-emitting layer (6), a hole blocking layer (7), an electron transport layer (8) and an electron injection layer (9);
wherein the light-emitting layer (6) contains a material made of the azafluorene spiroanthracene heterocyclic compound according to claim 1.
4. The organic electroluminescent element according to claim 3, wherein the hole blocking layer (7) and the electron transport layer (8) comprise a material made of the azafluorene spiroanthracene heterocyclic compound according to claim 1.
5. Use of the organic electroluminescent element as claimed in any one of claims 3 or 4 in an organic electroluminescent display device.
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