CN110452153A - Electroluminescent organic material and device - Google Patents

Electroluminescent organic material and device Download PDF

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CN110452153A
CN110452153A CN201810434641.6A CN201810434641A CN110452153A CN 110452153 A CN110452153 A CN 110452153A CN 201810434641 A CN201810434641 A CN 201810434641A CN 110452153 A CN110452153 A CN 110452153A
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高文正
张春雨
邵爽
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Beijing Eternal Material Technology Co Ltd
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Abstract

The present invention provides a kind of electroluminescent organic material and its application in the devices.A kind of organic compound is indicated by following general formula (1):Ar1For C6‑C30Aromatic ring or C3‑C30Hetero-aromatic ring remove the group that n+1 hydrogen obtains；Ar2Indicate one or two structure substituent group as shown in formula (2):X is selected from singly-bound, O, S, NR9Or CR10R11；R1Indicate Ar1N substituent group, separately selected from cyano, nitro, α by fluorine-substituted C1‑C10Alkyl ,-C (O) R12Or-C (O) NR13, n is the integer not less than 1；R2Selected from hydrogen, C1‑C10Alkyl, C3‑C10Naphthenic base, C1‑C10Alkoxy or cyano；R3‑R8One or any number of substituent groups are each independently represented, hydrogen, halogen ,-C (O) R are each independently selected from12、C1‑C10Alkyl, C3‑C10Naphthenic base, C1‑C10Alkoxy, C6‑C30Aryl, C3‑C30Heteroaryl, or combinations thereof；Adjacent any two substituent group can cyclization；R9‑R13Separately it is selected from C1‑C10Alkyl, C6‑C30Aryl or C3‑C30Heteroaryl；Have in molecule and only 1 C-N dicarbazyl group.

Description

Electroluminescent organic material and device
Technical field
The present invention relates to a kind of new Organic Electro Luminescent Materials, and its application in organic electroluminescence device, belong to In ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technique
Under conditions of electroexcitation, electroluminescent organic material can generate 25% singlet and 75% triplet state, Traditional fluorescent material can only utilize singlet exciton due to spin forbidden.In order to utilize triplet excitons, researcher Many methods are proposed, wherein being the most significantly the utilization of phosphor material.However phosphor material is since the T1 service life is generally in 1 μ s More than, significantly larger than service life of tens nanosecond of fluorescent material, therefore efficiency roll-off is serious at higher current densities, and due to making With rare heavy metal, material costly, therefore is unfavorable for the reduction of product cost.
Kyushu University professor Adachi discovery based on triplet state-singlet transition hot activation delayed fluorescence (TADF) material use amount of heat can realize reverse intersystem crossing of the energy from triplet excited states to singlet excited state, High-luminous-efficiency can be realized without using high-cost rare metal.In patent document 1, aurification strain formula meeting is lived by Nippon Steel Society and Kyushu University disclose a kind of material (referring to following formula) based on indolocarbazole, and disclose a kind of fluorescence and delay is glimmering The organic illuminating element of light type, which is characterized in that there is at least one luminescent layer to contain transmitting fluorescence and postpone glimmering on substrate The luminous organic material of light, the excited singlet state energy of the luminescent material and the difference of excited triplet state energy are 0~0.2eV, Indicate that compound illustrates higher efficiency performance.
The emphasis of the luminescence mechanism for thermal activation sensitization delayed fluorescence (TASF) that Tsinghua University professor Duan Lian proposes is will to swash State triplet energy state is sent out by upper conversion to excitation state singlet energy, then passes through Foxter energy transfer to dyestuff excitation state Singlet state, then realize it is luminous, to realize the separation of energy acquisition and luminescence process.Disclosing one kind in patent document 2 has Organic electroluminescence devices, including anode, hole transmission layer, luminescent layer, electron transfer layer and the cathode being stacked on one another, feature exists It is less than 0.15eV in the triplet state and singlet energy level difference of, the material of main part of luminescent layer, and adulterates in the material of main part glimmering Photoinitiator dye, and the singlet energy level of the fluorescent dye is lower than the singlet energy level of material of main part, realize high efficiency and Low efficiency roll-off and better excitation purity.
Currently, the material of main part of high triplet is concentrated mainly on cavity type carbazole compound (such as mCP and mCBP) and phosphorus Oxygroup class (such as DPEPO) main body.Have a plurality of TADF human subject material reports at present, such as patent document 3-6.
Existing technical literature:
Patent document 1:CN102648268B；
Patent document 2:CN 102709485B；
Patent document 3:WO2017190885A1；
Patent document 4:US2016071625A1；
Patent document 5:DE102016115854；
Patent document 6:US2016071625A1.
Summary of the invention
Problems to be solved by the invention
However, haveing the defects that when above-mentioned two human subjects application as follows: cavity type carbazoles material of main part is because of its electronics Transmittability is weaker and exciton is caused to be unevenly distributed, and device efficiency roll-offs seriously；Although phosphorus oxygen class compound material of main part has There is high efficiency, but since phosphorus-oxygen groups are unstable, causes device lifetime undesirable.Compound disclosed in above patent document The raising in device efficiency and service life cannot still be had both, therefore develop high triplet and stablize material of main part for the field OLED to Guan Chong It wants.In order to obtain high luminous efficiency in organic electroluminescence device, the efficiency roll-off of device is reduced, need to develop has height anti- To the material of intersystem crossing (RISC) rate.
Solution to problem
There is thermal activation delayed fluorescence the main purpose of the present invention is to provide a kind of organic electroluminescence device Can asymmetric organic compound, using its as the organic electroluminescence device of luminescent material and its organic electroluminescence hair The application of optical arena.
Specifically, shown in general structure of the invention such as formula (1):
Wherein:
Ar1For C6-C30Aromatic ring or C3-C30Hetero-aromatic ring remove the group that n+1 hydrogen obtains；
Ar2Indicate one or two structure substituent group as shown in formula (2):
X is selected from singly-bound, O, S, NR9Or CR10R11；
R1Indicate Ar1N substituent group, separately selected from cyano, nitro, α by fluorine-substituted C1-C10Alkyl, -C(O)R12Or-C (O) NR13, n is the integer not less than 1；
R2Selected from hydrogen, C1-C10Alkyl, C3-C10Naphthenic base, C1-C10Alkoxy or cyano；
R3-R8Any number of substituent groups for each independently representing one or allowing, are each independently selected from hydrogen, halogen ,-C (O)R12、 C1-C10Alkyl, C3-C10Naphthenic base, C1-C10Alkoxy, C6-C30Substituted or unsubstituted aryl, C3- C30Substituted or unsubstituted heteroaryl, or combinations thereof；Adjacent any two substituent group can cyclization；
X is NR9When R9, X CR10R11When R10And R11Separately it is selected from hydrogen, C1-C10Alkyl, C6-C30's Substituted or unsubstituted aryl or C3-C30Substituted or unsubstituted heteroaryl；
Have in molecule and only 1 C-N dicarbazyl group, the C-N dicarbazyl group in the application refers specifically to two carbazoles Group made of group is connected by C-N key；
When above-mentioned group is there are when substituent group, which is selected from halogen ,-C (O) R12、-C(O)NR13, cyano, nitro, C1-C10Alkyl, C3-C10Naphthenic base, C1-C10Alkoxy, C6-C30Aryl, C3-C30Heteroaryl or their group It closes；
R12And R13Separately it is selected from C1-C10Alkyl, C6-C30Aryl or C3-C30Heteroaryl.
The study found that above-mentioned organic compound good film-forming property of the invention, fluorescence quantum yield is high, is suitable as the master that shines Body material.Its principle is still not clear, and by inference may be following reason: in general formula (1) compound represented of the present invention, connection Ar1、 Ar2、R2Have and only one C-N dicarbazyl group on the phenyl ring of C-N dicarbazyl group, therefore it is asymmetric point Son, the crystallinity deterioration of molecule promote the rigidity of compound, and then raisingization so as to avoid intermolecular aggtegation The film forming and fluorescence quantum yield for closing object, are suitable as light emitting host material；On the other hand, organic compound of the invention In, electron-donating group and drawing electron group are adjusted the distribution of charges of compound, are conducive to by bridging bond collective effect The charge transfer state material that HOMO and LUM0 is spatially separating is formed, to adjust singlet-triplet of material, is improved RISC rate between energy system is realized and is passed through between the inverse system of energy, and emitting layer material use is suitable as.
In above-mentioned formula (1), Ar1Preferably C6-C18Aromatic ring or C3-C18Hetero-aromatic ring remove the group that n+1 hydrogen obtains, More preferably C6-C18Aromatic ring remove the group that n+1 hydrogen obtains, the most preferably group that indicates of following below formula,
R1Identical meaning is indicated with general formula (1),Phenyl ring and Ar in expression (1)1The site of connection.It needs to illustrate , in above-mentioned moieties (specifically, the 7th to the 15th group),Another aromatic ring is directed toward across an aromatic ring Center, refer to Ar1The site connecting with phenyl ring can be Ar1In any C on two aromatic rings；R1On extend --- It is similar, the center that an aromatic ring is directed toward another aromatic ring is passed through, refers to R1With Ar1The site of connection can be Ar1In two virtues Any C on ring.
In above-mentioned formula (1), X is preferably selected from singly-bound, O, S, more preferably singly-bound, that is, more preferably R7And R8Substituted carbazole Base.In above-mentioned formula (1), n is preferably 1,2 or 3, each R1Cyano, nitro, α are separately preferably selected from by fluorine-substituted C1- C8Alkyl, more preferably cyano, trifluoromethyl or nitro.
Studies have shown that having used the organic electroluminescent of the compounds of this invention when the compounds of this invention has above-mentioned group The current efficiency and external quantum efficiency of device have obtained very big improvement, while the service life of device is obviously improved.Its principle is still unknown It really, by inference may be after introducing supplied for electronic and electron-withdrawing group due to the compounds of this invention molecular skeleton, to pass through bridging The energy level of bond energy Effective Regulation compound, realization and the matched energy level data of adjacent materials, therefore device shows good property Energy.
In above-mentioned formula (1), R2It is preferably selected from hydrogen, C1-C8Alkyl, C3-C10Naphthenic base, C1-C8Alkoxy, cyano, More preferably hydrogen or cyano.In above-mentioned formula (1), R3And R4Preferably independently it is selected from hydrogen, C1-C8Alkyl, C6-C18Substitution or Unsubstituted aryl or C3-C18Substituted or unsubstituted heteroaryl, hydrogen, methyl, phenyl, pyridyl group are more preferably selected from, into one Step is preferably hydrogen or methyl, most preferably hydrogen.In above-mentioned formula (1), R5-R8It is preferred that each independently representing 1 group, respectively solely On the spot it is preferably selected from hydrogen, halogen ,-C (O) R12、C1-C8Alkyl, C3-C10Naphthenic base, C1-C8Alkoxy, C6-C18Take Generation or unsubstituted aryl, C3-C18Substituted or unsubstituted heteroaryl, be more preferably selected from hydrogen, fluorine, chlorine, methyl, ethyl, different Propyl, tert-butyl, methoxyl group, phenyl, pyridyl group are further preferably selected from hydrogen, methyl, isopropyl, tert-butyl, most preferably Hydrogen.R9、R10And R11Preferably independently it is selected from hydrogen, C1-C8Alkyl, C6-C18Substituted or unsubstituted aryl or C3-C18Take Generation or unsubstituted heteroaryl.R12And R13Preferably independently it is selected from C1-C8Alkyl, C6-C18Aryl or C3-C18Heteroaryl Base.
Further, the organic compound that formula of the invention (1) indicates can be preferably in detail below in structure P1-P100 One kind, but these compounds are only representative.
The present invention also provides above compounds in organic electroluminescence device as the application of emitting layer material.It is specific and Speech, above compound may be used as luminescent layer material of main part, be also used as luminescent layer dyestuff.
The present invention also provides a kind of organic electroluminescence devices, including the first electrode being located on substrate and the second electricity Pole, and the organic layer including at least one layer of luminescent layer between electrode.Wherein, above-mentioned chemical combination is contained in luminescent layer Object.
One embodiment of the invention provides a kind of organic electroluminescence device, including first electrode, second electrode And one or more layers organic layer being inserted between the first electrode and second electrode.
Further, as the organic layer between first electrode and second electrode, electron injecting layer is generally comprised, electronics passes The organic layers such as defeated layer, luminescent layer, hole transmission layer, hole injection layer.
Next, organic electroluminescence device is described in detail.
Organic electroluminescence device includes the first electrode and second electrode on substrate, and between electrode Including at least the organic layer of one layer of luminescent layer, the organic layer can be multilayered structure.For example, the organic material layer may include Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer.
Substrate using substrate used in organic light emitting display, such as: glass, polymer material and have TFT member device Glass and polymer material of part etc..
Anode material can use indium tin oxygen (ITO), indium zinc oxygen (IZO), stannic oxide (SnO2), zinc oxide (ZnO) etc. Transparent conductive material is also possible to the metal materials such as silver and its alloy, aluminium and its alloy, is also possible to the organic conductives such as PEDOT The multilayered structure of material and above-mentioned material.
It can also include the hole injection layer between hole transmission layer and anode in device, it is including but not limited to following The one or more combinations for the HI1-HI3 enumerated.
Hole transmission layer can be, but not limited to one or more combinations of following enumerated HT1-HT31.
Luminescent layer material of main part can be, but not limited to one or more combinations of following enumerated TDH1-TDH24.
Dyestuff can be, but not limited to one or more combinations of following enumerated PD1-PD17.
Dyestuff can with but be not limited to one or more combinations of following enumerated FD1-FD18.
Electron transfer layer can be, but not limited to one or more combinations of following enumerated ET1-ET57.
It can also include the electron injecting layer between electron transfer layer and cathode, electron injecting layer material packet in device It includes but is not limited to the following one or more combinations enumerated.
LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca.
Cathode is metals, metal mixture, the oxide such as magnesium silver mixture, LiF/A1, ITO.
Invention effect
Compound good film-forming property represented by general formula (1) of the invention, fluorescence quantum yield is high, is suitable as luminescent layer material Material.The organic electroluminescence device of the compounds of this invention has been used to show good performance, current efficiency and outer quantum effect Rate is greatly improved, while the service life is obviously improved.
Specific embodiment
In order to further deepen the understanding of the present invention, below with reference to synthetic example and device embodiments, to the present invention Compound be further explained explanation.
Synthetic example
The synthesis that synthetic method in synthetic example is carried out using Suzki coupling reaction and substitution reaction.
Synthesis example 1: the synthesis of product P1
The synthesis of intermediate M1
Under nitrogen atmosphere, by bromo- 2, the 6- difluorobenzonilyile 2.2g (10.0mmol, 1eq) of 4-, 4- cyanophenylboronic acid 1.8g (12.0mmol, 1.2eq), Pd (PPh3)40.16g (0.1mmol, 1%eq), potassium carbonate 4.1g (30.0mmol, 3eq) are added to 20mL toluene, 5mL ethyl alcohol and 5mL water is being added in 100mL single port bottle, is warming up to reflux temperature, reaction is overnight.Use silica gel column layer Analysis method.Obtain M1, mass spectrum: 240.
The synthesis of intermediate M2
Under nitrogen atmosphere, 3,9- is joined into carbazole 3.3g (10.0mmol, 1.0eq), NaHH 0.24g (10.0mmol, 1.0eq), DMF (30mL) is added to 100mL single port bottle and intermediate M1 2.4g is added after stirring 30min under the conditions of ice-water bath (10.0mmol, 1eq) is warming up to room temperature, and reaction is overnight.Use silica gel column chromatography.Obtain M2, mass spectrum: 552.
The synthesis of product P1
By reactant 3,9- connection carbazole replaces with carbazole and reacts with intermediate M2, by with intermediate M2 phase in synthesis example 1 Same synthetic method, obtains P1, mass spectrum: 699.1H_NMR (300MHz, CDCl3): 8.60 (3H), 8.30 (2H), 8.15 (2H), 7.98 (1H), 7.94 (3H), 7.87 (2H), 7.80 (2H), 7.66 (3H), 7.53 (2H), 7.36 (3H), 7.33 (1H), 7.31 (2H), 7.28 (3H).
Synthesis example 2: the synthesis of product P12
The synthesis of intermediate M3
Bromo- 2, the 6- difluorobenzonilyile of reactant 4- is replaced with into iodo- 5, the 6- difluorobenzonilyile of the bromo- 4- of 2-, by in synthesis example 1 The identical synthetic method of intermediate M1, obtains M3, mass spectrum: 319.
The synthesis of intermediate M4
Under nitrogen atmosphere, by intermediate M33.2g (10.0mmol, leq), 3,9- connection carbazole 3.7g (11.0mmol, 1.1eq), Pd2(dba)30.09g (0.1mmol, 1%eq), potassium tert-butoxide 2.9g (30.0mmol, 3eq) are added to 100mL single port 20mL dimethylbenzene is being added in bottle, is warming up to reflux temperature, reaction is overnight.Use silica gel column chromatography.Obtain M4, mass spectrum: 240.
The synthesis of product P12
By reactant 3,9- connection carbazole replaces with carbazole and reacts with intermediate M4, by with intermediate M2 phase in synthesis example 1 Same synthetic method, obtains P12, mass spectrum: 864.1H NMR (300MHz, CDCl3): 8.60 (4H), 8.30 (1H), 8.15 (3H), 7.98 (1H), 7.94 (5H), 7.87 (2H), 7.80 (4H), 7.66 (3H), 7.53 (4H), 7.36 (3H), 7.33 (1H), 7.31 (3H), 7.28 (4H).
Synthesis example 3: the synthesis of product P23
The synthesis of intermediate M5
Reactant 4- cyanophenylboronic acid is replaced with into 4- trifluoromethylbenzene boronic acid, by with intermediate M1 phase in synthesis example 1 Same synthetic method, obtains M5, mass spectrum: 283.
The synthesis of intermediate M6
Reactant intermediate M1 is replaced with into intermediate M5, by synthetic method identical with intermediate M2 in synthesis example 1, Obtain M6, mass spectrum: 595.
The synthesis of product P23
By reactant 3,9- connection carbazole replaces with carbazole and reacts with intermediate M6, by with intermediate M2 phase in synthesis example 1 Same synthetic method, obtains P23, mass spectrum: 742.1H NMR (300MHz, CDCl3): 8.60 (3H), 8.30 (2H), 8.15 (2H), 7.98 (1H), 7.94 (3H), 7.71 (2H), 7.66 (3H), 7.53 (4H), 7.41 (2H), 7.36 (3H), 7.33 (1H), 7.31 (2H), 7.28 (3H).
Synthesis example 4: the synthesis of product P34
The synthesis of intermediate M7
Bromo- 2, the 6- difluorobenzonilyile of reactant 4- is replaced with into bromo- 3, the 5- difluorobenzene of 1-, by with intermediate in synthesis example 1 The identical synthetic method of M1, obtains M7, mass spectrum: 215.
The synthesis of intermediate M8
Reactant intermediate M1 is replaced with into intermediate M7, by synthetic method identical with intermediate M2 in synthesis example 1, Obtain M8, mass spectrum: 527.
The synthesis of product P34
By reactant 3,9- connection carbazole replaces with carbazole and reacts with intermediate M8, by with intermediate M2 phase in synthesis example 1 Same synthetic method, obtains P34, mass spectrum: 674.1H NMR (300MHz, CDCl3): 8.60 (3H), 8.15 (2H), 8.11 (2H), 7.98 (1H), 7.94 (3H), 7.87 (2H), 7.80 (2H), 7.66 (3H), 7.53 (2H), 7.43 (1H), 7.36 (3H), 7.33 (1H), 7.31 (3H), 7.28 (3H).
Synthesis example 5: the synthesis of product P39
The synthesis of intermediate M9
Bromo- 2, the 6- difluorobenzonilyile of reactant 4- is replaced with into bromo- 3, the 5- difluorobenzene of 1-, 4- cyanophenylboronic acid is replaced with 3, 4,5- tricyano phenylboric acids obtain M9, mass spectrum: 265 by synthetic method identical with intermediate M1 in synthesis example 1.
The synthesis of intermediate M10
Reactant intermediate M1 is replaced with into intermediate M9, by synthetic method identical with intermediate M2 in synthesis example 1, Obtain M10, mass spectrum: 577.
The synthesis of product P39
By reactant 3,9- connection carbazole replaces with carbazole and reacts with intermediate M10, by with intermediate M2 phase in synthesis example 1 Same synthetic method, obtains P39, mass spectrum: 749.1H NMR (300MHz, CDCl3): 8.60 (3H), 8.21 (2H), 8.15 (2H), 8.10 (2H), 7.98 (1H), 7.66 (3H), 7.53 (2H), 7.43 (1H), 7.36 (3H), 7.33 (1H), 7.31 (2H), 7.28 (3H)。
Synthesis example 6: the synthesis of product P56
The synthesis of intermediate M11
Bromo- 2, the 6- difluorobenzonilyile of reactant 4- is replaced with into 3,4,5- trinitro- -1- bromobenzenes, 4- cyanophenylboronic acid is replaced M11 is obtained, mass spectrum: 325 by synthetic method identical with intermediate M1 in synthesis example 1 for 3,5- difluoro phenyl boric acid.
The synthesis of intermediate M12
Reactant intermediate M1 is replaced with into intermediate M11, by synthesis side identical with intermediate M2 in synthesis example 1 Method obtains M12, mass spectrum: 637.
The synthesis of product P56
By reactant 3,9- connection carbazole replaces with carbazole and reacts with intermediate M12, by with intermediate M2 phase in synthesis example 1 Same synthetic method, obtains P56, mass spectrum: 809.1H NMR (300MHz, CDCl3): 9.33 (2H), 8.60 (3H), 8.15 (2H), 8.10 (2H), 7.98 (1H), 7.94 (3H), 7.66 (3H), 7.53 (2H), 7.43 (1H), 7.36 (3H), 7.33 (1H), 7.31 (2H), 7.28 (3H).
Device embodiments
The 1-6 and comparative example 1-2 compound that the present invention will be described in detail synthesizes is applied in the devices by the following examples The effect of luminescent layer dyestuff；The compound that embodiment 7-8 and comparative example 3-4 illustrates that the present invention synthesizes is applied to shine in the devices The effect of layer sensitizer；The manufacture craft of the device is identical, and uses identical baseplate material and electrode material, electrode material The film thickness of material is also consistent, except that the emitting layer material of device is changed.Used compound molecule formula is such as Under:
Embodiment 1
Organic electroluminescence device preparation process is as follows:
The glass plate for being coated with transparent conductive layer is ultrasonically treated in commercial detergent, is rinsed in deionized water, In acetone: ultrasonic oil removing in alcohol mixed solvent is baked under clean environment and completely removes moisture content, clear with ultraviolet light and ozone It washes, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, above-mentioned Vacuum evaporation HI-2 is as hole injection layer on anode tunic, and evaporation rate 0.1nm/s, vapor deposition film thickness is 10nm；
Hole transmission layer of the vacuum evaporation HT-2 as device on hole injection layer, evaporation rate 0.1nm/s steam Plating total film thickness is 40nm；
Second hole transmission layer of the vacuum evaporation HT-28 as device, evaporation rate are on hole transmission layer 0.1nm/s, vapor deposition total film thickness are 20nm；
The luminescent layer of vacuum evaporation device on hole transmission layer, luminescent layer include material of main part and dye materials, benefit The method steamed altogether with multi-source, adjusting material of main part TDH14 evaporation rate are 0.1nm/s, and 20% ratio of dyestuff P1 evaporation rate is set Fixed, vapor deposition total film thickness is 30nm；
The electron transport layer materials ET-34 of vacuum evaporation device, evaporation rate 0.1nm/s on luminescent layer steam Plating total film thickness is 30nm；
On electron transfer layer (ETL) vacuum evaporation with a thickness of the LiF of 0.5nm as electron injecting layer, with a thickness of 150mm Cathode of the A1 layer as device.
Method as described above prepares following device, makes it have with flowering structure:
Embodiment 2:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH14:20%P12 (30nm)/ET- 34(20nm)/LiF(0. 5nm)/Al(150nm)
Wherein 5% expression P12 is 20% relative to the weight ratio of TDH14, and following embodiment is also expressed in this way.
Embodiment 3:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH14:20%P23 (30nm)/ET- 34(20nm)/LiF(0. 5nm)/Al(150nm)
Embodiment 4:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH14:20%P34 (30nm)/ET- 34(20nm)/LiF(0. 5nm)/Al(150nm)
Embodiment 5:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH14:20%P39 (30nm)/ET- 34(20nm)/LiF(0. 5nm)/Al(150nm)
Embodiment 6:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH14: 20%P56 (30nm)/ET- 34(20nm)/LiF(0. 5nm)/Al(150nm)
Embodiment 7:
Method as described above prepares device, the difference is that luminescent layer includes material of main part, sensitization agent material And dye materials, the method steamed altogether using multi-source, adjusting material of main part TDH-14 evaporation rate are 0.1nm/s, sensitizer P1's The 20% of material evaporation rate based on evaporation rate, 3% ratio of material evaporation rate based on the evaporation rate of dyestuff FD-14 Example setting, vapor deposition total film thickness are 30nm；It makes it have with flowering structure:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH-14: 20%P1:3%FD-14 (30nm)/ET-3 4(20nm)/LiF(0.5nm)/Al(150nm)
Embodiment 8:
Method as described above prepares device, the difference is that luminescent layer includes material of main part, sensitization agent material And dye materials, the method steamed altogether using multi-source, adjusting material of main part TDH14 evaporation rate are 0.1nm/s, sensitizer P12's The 20% of material evaporation rate based on evaporation rate, 3% ratio of material evaporation rate based on the evaporation rate of dyestuff PD-1 Example setting, vapor deposition total film thickness are 30nm；It makes it have with flowering structure:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH-14: 20%P12: 3%PD-1 (30nm)/ET-3 4(20nm)/LiF(0.5nm)/Al(150nm)
Comparative example 1:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH14: 20%CC-1 (30nm)/ET- 34(20nm)/ LiF(0.5nm)/Al(150nm)
Comparative example 2:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH14: 20%CC-2 (30nm)/ET- 34(20nm)/ LiF(0.5nm)/Al(150nm)
Comparative example 3:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH-14: 20%CC-2: 3%FD-14 (30nm)/ET -34(20nm)/LiF(0.5nm)/Al(150nm)
Comparative example 4:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/HT-28 (20nm)/TDH-14: 20%CC-2: 3%PD-1 (30nm)/ET- 34(20nm)/LiF(0.5nm)/Al(150nm)
Following performance measurement is carried out to the organic electroluminescence device prepared by the above process:
Under same brightness, is measured in Examples 1 to 8 and comparative example 1 and be prepared using digital sourcemeter and luminance meter Organic electroluminescence device driving voltage and current efficiency.Specifically, promoting voltage, measurement with the rate of 0.1V per second When the brightness of organic electroluminescence device reaches 1000cd/m2When voltage, that is, driving voltage, while the electric current measured at this time is close Degree；The ratio of brightness and current density is current efficiency.
The organic electroluminescence device performance obtained produced above see the table below:
By embodiment 1-6 and comparative example 1-2 comparison as it can be seen that the compound that the present invention synthesizes is applied to shine in the devices Either efficiency or service life all obtains larger change than known OLED material when layer dyestuff, and especially life-span upgrading is obvious；It is real Apply a 7-8 and when compound that the comparative example 3-4 comparative illustration present invention synthesizes is applied to luminescent layer sensitizer in the devices, it can With effective sensitizing dyestuff, it is able to achieve effective energy transmission, to obtain excellent device performance.
Although the present invention is described in conjunction with the embodiments, the present invention is not limited to the above embodiments, should manage Solution, under the guidance of present inventive concept, those skilled in the art can carry out various modifications and improve, and appended claims summarise The scope of the present invention.

Claims (10)

1. a kind of organic compound is indicated by following general formula (1):
Wherein:
Ar1For C6-C30Aromatic ring or C3-C30Hetero-aromatic ring remove the group that n+1 hydrogen obtains；
Ar2Indicate one or two structure substituent group as shown in formula (2):
X is selected from singly-bound, O, S, NR9Or CR10R11；
R1Indicate Ar1N substituent group, separately selected from cyano, nitro, α by fluorine-substituted C1-C10Alkyl ,-C (O)R12Or-C (O) NR13, n is the integer not less than 1；
R2Selected from hydrogen, C1-C10Alkyl, C3-C10Naphthenic base, C1-C10Alkoxy or cyano；
R3-R8Any number of substituent groups for each independently representing one or allowing, are each independently selected from hydrogen, halogen ,-C (O) R12、C1-C10Alkyl, C3-C10Naphthenic base, C1-C10Alkoxy, C6-C30Substituted or unsubstituted aryl, C3-C30's Substituted or unsubstituted heteroaryl, or combinations thereof；Adjacent any two substituent group can cyclization；
X is NR9When R9, X CR10R11When R10And R11Separately it is selected from C1-C10Alkyl, C6-C30Substitution or not Substituted aryl or C3-C30Substituted or unsubstituted heteroaryl；
Have in molecule and only 1 C-N dicarbazyl group；
When above-mentioned group is there are when substituent group, which is selected from halogen ,-C (O) R12、-C(O)NR13, cyano, nitro, C1-C10 Alkyl, C3-C10Naphthenic base, C1-C10Alkoxy, C6-C30Aryl, C3-C30Heteroaryl or their combination；
R12And R13Separately it is selected from C1-C10Alkyl, C6-C30Aryl or C3-C30Heteroaryl.
2. organic compound according to claim 1, wherein Ar1For following below formula indicate group,
Indicate phenyl ring and Ar1The site of connection.
3. organic compound according to claim 1, wherein X is selected from singly-bound, O, S.
4. organic compound according to claim 1, wherein n 1,2 or 3, each R1Separately it is selected from cyano, trifluoro Methyl or nitro.
5. organic compound according to claim 1, wherein R5-R81 substituent group is each independently represented, respectively solely On the spot it is selected from hydrogen, methyl, isopropyl, tert-butyl.
6. organic compound according to any one of claims 1 to 5, wherein the C-N dicarbazyl group is following knot One of structure:
7. organic compound according to claim 6 is one of following compound P1~P100:
8. application of the organic compound described in claim 1~7 in organic electroluminescence device.
9. a kind of organic electroluminescence device, including the first electrode and second electrode being located on substrate, and be located at electrode it Between the organic layer including at least one layer of luminescent layer, which is characterized in that containing described in claim 1~7 in the luminescent layer Organic compound.
10. organic electroluminescence device according to claim 9, wherein organic compound described in claim 1~7 As material of main part.
CN201810434641.6A 2018-05-08 2018-05-08 Electroluminescent organic material and device Pending CN110452153A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110407832A (en) * 2018-04-26 2019-11-05 北京鼎材科技有限公司 A kind of Anthraquinones electroluminescent organic material and its application
CN110407825A (en) * 2018-04-26 2019-11-05 北京鼎材科技有限公司 A kind of Anthraquinones electroluminescent organic material and its application
CN111100060A (en) * 2019-12-11 2020-05-05 江苏大学 Carbazole thermal activation delayed fluorescent material and preparation method thereof
CN111825660A (en) * 2019-04-19 2020-10-27 北京鼎材科技有限公司 Compound, thermal activation delayed fluorescence material, organic electroluminescent device and application
WO2023171761A1 (en) * 2022-03-10 2023-09-14 国立大学法人京都大学 Dicarbazolyl compound and organic electroluminescence element

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110407832A (en) * 2018-04-26 2019-11-05 北京鼎材科技有限公司 A kind of Anthraquinones electroluminescent organic material and its application
CN110407825A (en) * 2018-04-26 2019-11-05 北京鼎材科技有限公司 A kind of Anthraquinones electroluminescent organic material and its application
CN111825660A (en) * 2019-04-19 2020-10-27 北京鼎材科技有限公司 Compound, thermal activation delayed fluorescence material, organic electroluminescent device and application
CN111100060A (en) * 2019-12-11 2020-05-05 江苏大学 Carbazole thermal activation delayed fluorescent material and preparation method thereof
WO2023171761A1 (en) * 2022-03-10 2023-09-14 国立大学法人京都大学 Dicarbazolyl compound and organic electroluminescence element

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