WO2016197353A1 - Composé organique électroluminescent et dispositif organique électroluminescent le comprenant - Google Patents

Composé organique électroluminescent et dispositif organique électroluminescent le comprenant Download PDF

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WO2016197353A1
WO2016197353A1 PCT/CN2015/081225 CN2015081225W WO2016197353A1 WO 2016197353 A1 WO2016197353 A1 WO 2016197353A1 CN 2015081225 W CN2015081225 W CN 2015081225W WO 2016197353 A1 WO2016197353 A1 WO 2016197353A1
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group
substituted
unsubstituted
electron
compound
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PCT/CN2015/081225
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Sang Hee Cho
Hong Yeop NA
Zhengming TANG
Shaoguang Feng
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Dow Global Technologies Llc
Rohm And Haas Electronic Materials Korea Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/166—Electron transporting layers comprising a multilayered structure

Definitions

  • the present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
  • a low molecular green light-emitting organic electroluminescent (EL) device was developed by Tang, etc., of Eastman Kodak in 1987 by using TPD/ALq 3 bi-layer consisting of a light-emitting layer and an electron transport layer. Thereafter, the development of organic EL devices was rapidly effected and the devices were currently commercialized. Current organic EL devices mostly use phosphorescent materials with excellent luminous efficiency for panel manufacture. In the case of red and green light-emitting organic EL devices, commercialization of organic EL devices by using phosphorescent materials was succeeded.
  • the first problem is that if the materials are exposed at high temperature in the process of panel production, current property of the devices changes, and thus light-emitting luminance may be accordingly changed. Furthermore, in view of structural feature, interface property between a light-emitting layer and an electron injection layer is declined, and thus luminance of the devices may be decreased. Also, fluorescent light-emitting materials have lower efficiency characteristics than phosphorescent light-emitting materials. Thus, in order to improve efficiency, specific fluorescent light-emitting materials such as the combination of an anthracene-based host and a pyrene-based dopant were used.
  • Korean Patent Application Laying-Open No. 10-2012-0092550 discloses an organic EL device comprising a blocking layer disposed between an electron injection layer and a light-emitting layer, wherein the blocking layer includes aromatic heterocyclic derivatives comprising an azine ring.
  • the literature does not recite an organic EL device using the compounds comprising an oxazole or thiazole skeleton in an electron buffer layer.
  • Japanese Patent No. 4947909 contains a blue fluorescent light-emitting device comprising an electron buffer layer.
  • the device had the insertion of an electron buffer layer, thereby efficiently injecting electrons into a light-emitting layer compared with Alq 3 and controlling movement of electrons. This feature inhibited decrease of driving voltage and deterioration of a light-emitting interface, and thus lifespan of the device was improved.
  • materials of an electron buffer layer are limited to Alq 3 derivatives, restriction of electrons is the purpose, and types of materials are not various, and thus analysis for effective luminous efficiency and lifespan improvement is limited.
  • Korean Patent Application Laying-Open No. 10-2014-0086861 discloses an organic EL device having the insertion of an electron transport layer including quinoline-benzoxazole derivatives.
  • the electron transport layer only plays a role as an electron transport layer co-deposited with lithium quinolate.
  • the literature has limitation in optimizing devices comprising an electron buffer layer in view of control of electron current property by using pure characteristics of related compounds.
  • the object of the present invention is to provide an organic EL device having low driving voltage and high luminous efficiency.
  • Ar 1 represents a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 5-to 30-membered heteroaryl group;
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30) arylene group, or a substituted or unsubstituted 3-to 30-membered heteroarylene group;
  • X represents O, S, or NR 2 ;
  • R 1 and R 2 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C3-C30) cycloalkyl group, a substituted or unsubstituted (C3-C30) cycloalkenyl group, a substituted or unsubstituted 3-to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted 3-to 30-membered heteroaryl group, -NR 3 R 4 , or -SiR 5 R 6 R 7 ; or are linked to an adjacent substituent (s) to form a substituted or unsubstituted mono-or polycyclic (C3-C30) ali
  • R 3 to R 7 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C3-C30) cycloalkyl group, a substituted or unsubstituted (C3-C30) cycloalkenyl group, a substituted or unsubstituted 3-to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 3-to 30-membered heteroaryl group;
  • a represents an integer of 1 to 4; where a is an integer of 2 or more, each R 1 may be the same or different; and
  • the organic EL device according to the present invention comprises an electron buffer layer, thereby controlling injection of electrons and improving characteristics of interface disposed between a light-emitting layer and an electron injection layer.
  • the present invention can provide an organic EL device with excellent luminous efficiency.
  • an electron buffer layer is present between a light-emitting layer and an electron transport layer, electron current is inhibited, and thus driving voltage may be increased and efficiency may be decreased.
  • driving voltage may be increased and efficiency may be decreased.
  • an organic EL device with low driving voltage, excellent luminous efficiency such as current efficiency and power efficiency, and implementation possibility of high purity color may be provided by rapid election injection characteristics and improvement of interface property.
  • Figure 1 shows one embodiment of the structure of the organic EL device comprising an electron buffer layer according to the present invention.
  • Figure 2 shows an energy diagram of the organic EL device comprising an electron buffer layer according to the present invention.
  • Figure 3 shows graphs of current efficiency (cd/A) vs. luminance (cd/m 2 ) of the organic EL devices which are respectively produced according to Device Example 2 and Comparative Example 1.
  • the compound of formula 1 is represented by one of the following formulae 2 to 5:
  • L 1 , X, R 1 , and a are as defined in formula 1;
  • X 2 represents N or CR 8 ;
  • X 3 represents N or CR 9 ;
  • R 8 to R 11 each independently have the same meaning as the definition of R 3 of formula 1;
  • Ar 2 has the same meaning as the definition of Ar 1 of formula 1;
  • R 12 has the same meaning as the definition of R 1 of formula 1;
  • Ar 3 and Ar 4 have the same meaning as the definition of Ar 1 of formula 1;
  • X 4 represents N or CR 13 ;
  • R 13 has the same meaning as the definition of R 1 of formula 1;
  • R 14 has the same meaning as the definition of R 1 of formula 1;
  • (C1-C30) alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • (C2-C30) alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30) alkynyl is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • (C1-C30) alkoxy is meant to be a linear or branched alkoxy having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methoxy, ethoxy, propoxy, isopropoxy, 1-ethylpropoxy, etc.
  • “ (C3-C30) cycloalkyl” is a mono-or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • (C6-C30) aryl (ene) is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e. a substituent.
  • Substituents of the substituted alkyl group, the substituted aryl (ene) group, the substituted heteroaryl (ene) group, the substituted cycloalkyl group, the substituted cycloalkenyl group, the substituted heterocycloalkyl group, or the substituted mono-or polycyclic (C3-C30) alicyclic or aromatic ring in formula 1 are each independently at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30) alkyl group; a halo (C1-C30) alkyl group; a (C2-C30) alkenyl group;
  • the organic EL compound of formula 1 may be selected from the group consisting of the following compounds, but is not limited thereto:
  • the present invention relates to the organic EL compound represented by formula 1 and an organic EL device comprising the same.
  • the organic EL device of the present invention comprises a first electrode, a second electrode opposing the first electrode, a light-emitting layer disposed between the two electrodes, and an electron transport zone and an electron buffer layer disposed between the light-emitting layer and the second electrode, wherein the electron buffer layer may comprise the compound represented by formula 1.
  • driving voltage and efficiency of the device may be improved.
  • An electron buffer layer can be used to solve the problem that when the devices are exposed at high temperature in the process of panel production, current property of the devices changes, and light-emitting luminance may be accordingly changed.
  • the characteristics of compounds which are included in an electron buffer layer are important to secure devices with similar current property to devices free from an electron buffer layer and stability for exposure at high temperature.
  • the compound represented by formula 1 is a benzoxazole-based, benzothiazole-based, or benzoimidazole-based compound, and has excellent thermal stability and is an electron-rich group having strong electronegativity.
  • the compound was mainly used as a light-emitting layer material, or in an electron-transport layer and a hole blocking layer.
  • the literature specifically discloses characteristics and use of the corresponding derivatives (see Current Applied Physics., 5, 2005, 75; US 2004/0234809 A1 and US 2011/0196158 A1) . Furthermore, the literature recites that intramolecular hydrogen bonding by using polarity property of Zn complexes and benzothiazole ligands in the corresponding derivatives results in excited-state intramolecular proton transfer (ESIPT) which is a type of energy transfer, and thus the derivatives are used in an electron-transport layer (see Adv. Funct. Mater., 2009, 19, 1663) . However, none of the literature refer to the use of an electron buffer layer.
  • ESIPT excited-state intramolecular proton transfer
  • the present invention places emphasis on driving at low voltage, efficiency improvement, and thermal stability of the devices by using optimized LUMO (lowest unoccupied molecular orbital) energy values and great electron current property of the respective corresponding compounds rather than of hole-blocking ability of the corresponding compounds as an electron-transport layer.
  • LUMO lowest unoccupied molecular orbital
  • the compounds of the present invention have a molecular sieve size of 3 and thus can be produced through simple synthesis procedure, have competitive yield and price, and have easy intermolecular electron transition due to large intramolecular overlap by small size of a molecular sieve.
  • the intermolecular stacking strengthens, the horizontal molecular orientation is easy, and thus realization of rapid electron current property may be possible.
  • the compounds according to the present invention can greatly contribute driving at low voltage, and improvement of efficiency and lifespan of organic EL devices.
  • Such improvement of device characteristics is greatly effective in securing stability for exposure to high temperature in the process of panel production and improving performance of devices.
  • electron injection may be controlled by electron affinity LUMO energy value of an electron buffer layer by inserting the electron buffer layer between a light-emitting layer and the second electrode.
  • LUMO energy value and HOMO (highest occupied molecular orbital) energy value have inherently a negative number, but LUMO energy value and HOMO energy value in the present invention are conveniently expressed in their absolute values. Furthermore, the comparison between LUMO energy values is based on their absolute values. LUMO energy value and HOMO energy value in the present invention are calculated by Density Functional Theory (DFT) .
  • DFT Density Functional Theory
  • LUMO energy value of the electron buffer layer may be larger than that of the host compound.
  • the difference in LUMO energy values of the electron buffer layer and the host compound may be specifically 0.2 to 0.3 eV or less.
  • LUMO energy values of the electron buffer layer and the host compound may be 1.8 to 1.9 eV and 1.6 eV, respectively, and the difference in their LUMO energy values may be 0.2 to 0.3 eV.
  • LUMO barrier between the host compound and the electron buffer layer may be a factor in increasing driving voltage, when the compound represented by formula 1 is included in the electron buffer layer, it makes it easier to transport electrons to the host compound compared with other compounds. Therefore, the organic EL device of the present invention may have low driving voltage, excellent luminous efficiency, and long lifespan.
  • LUMO energy values in the electron buffer layer represent specifically LUMO energy values of the compound represented by formula 1 included in the electron buffer layer.
  • the electron transport zone means the zone transports electrons from the second electrode to the light-emitting layer.
  • the electron transport zone may comprise an electron transport compound, a reducing dopant, or the combination thereof.
  • the electron transport compound may be at least one selected from the group consisting of oxazole-based compounds, isoxazole-based compounds, triazole-based compounds, isothiazole-based compounds, oxadiazole-based compounds, thiadiazole-based compounds, perylene-based compounds, anthracene-based compounds, aluminum complexes, and gallium complexes.
  • the reducing dopant may be at least one selected from the group consisting of an alkaline metal, an alkaline metal compound, an alkaline earth metal, a rare-earth metal, halides thereof, oxides thereof, and complexes thereof.
  • the electron transport zone may comprise an electron transport layer, an electron injection layer, or both of them. Respective electron transport layer and electron injection layer may consist of two or more layers.
  • LUMO energy value of the electron buffer layer may be lower or higher than that of the electron transport zone. For example, LUMO energy values of the electron buffer layer and the electron transport zone may be 1.9 eV and 1.8 eV, respectively, and the difference in their LUMO energy values may be 0.1 eV.
  • the electron buffer layer Since the electron buffer layer has the LUMO energy value above, electrons can be easily injected to the light-emitting layer through the electron buffer layer.
  • LUMO energy value of the electron transport zone may be 1.7 eV and higher or 1.9 eV and higher.
  • LUMO energy values of the electron buffer layer and the electron transport layer may be 1.7 eV and 1.9 eV, respectively, and the difference in their LUMO energy values may be 0.2 eV.
  • the barrier is present between the electron buffer layer and the electron transport layer, if the compound of the present invention is used in the electron buffer layer, rapid electron current property may be realized.
  • LUMO energy values of the electron buffer layer may be higher than those of the host compound and the electron transport zone.
  • LUMO energy values may have the relationship of the electron buffer layer > the electron transport zone > the host compound.
  • electrons may be restricted between the light-emitting layer and the electron buffer layer and electron injection may be hindered, and thus driving voltage may be increased.
  • the electron buffer layer having the compound of formula 1 easily transports electrons to the light-emitting layer, and thus the organic EL device of the present invention may have low driving voltage, excellent luminous efficiency, and long lifespan.
  • the LUMO energy values can be easily measured according to various known processes.
  • the LUMO energy values can be commonly determined by using cyclic voltammetry or ultraviolet photoelectron spectroscopy (UPS) .
  • UPS ultraviolet photoelectron spectroscopy
  • one skilled in the art can embody the present invention by easily understanding the electron buffer layer, the host compound, and the electron transport zone which satisfy the relations of LUMO energy values according to the present invention.
  • HOMO energy values can be easily measured in the same manner as LUMO energy values.
  • Acetonitrile (60.0 mL) was added to a mixture of tetrachloropyridine (2.17 g, 10.0 mmol, 217.0 g/mol) , phenylboronic acid (2.56 g, 21.0 mmol, 122.0 g/mol) , K 2 CO 3 (2.76 g, 20.0 mmol, 138.0 g/mol, 2M in deionized water) , and tetrakis (triphenylphosphine) palladium (O) (Pd (PPh 3 ) 4 ) (58.0 mg, 0.05 mmol, 1155.0 g/mol) in a two-neck flask under N 2 atmosphere, and then the mixture was stirred under reflux for 4 hrs. The reaction results were monitored by using Thin-layer chromatography (TLC) . After cooling the mixture to room temperature, white crystals were precipitated from the solution. The crystals were filtered and directly used in a next step.
  • TLC Thin-layer chromat
  • Dioxane (150.0 mL) was added to a mixture of compound 1-1 (3.00 g, 10.0 mmol, 300.0 g/mol) , compound 1-2 (7.08 g, 21.0 mmol, 337.0 g/mol) , K 3 PO 4 (4.45 g, 21.0 mmol, 212.0 g/mol, 2M in deionized water) , palladium (II) acetate (Pd (OAc) 2 ) (22.0 mg, 0.1 mmol, 224.0 g/mol) , and X-Phos (48.0 mg, 0.1 mmol, 476.0 g/mol) in a two-neck flask under N 2 atmosphere, and then the mixture was stirred under reflux for 12 hrs. The reaction results were monitored by TLC. After cooling the mixture to room temperature, the residue was purified with silica gel and recrystallized to obtain white powder as a final product.
  • Acetonitrile (60.0 mL) was added to a mixture of tetrachloropyridine (2.17 g, 10.0 mmol, 217.0 g/mol) , naphthalene-2-yl-boronic acid (3.61 g, 21.0 mmol, 172.0 g/mol) , K 2 CO 3 (8.70 g, 63.0 mmol, 138.0 g/mol, 2M in deionized water) , and Pd (PPh 3 ) 4 (58.0 mg, 0.05 mmol, 1155.0 g/mol) in a 250 mL two-neck flask under N 2 atmosphere, and then the mixture was stirred under reflux for 4 hrs. The reaction results were monitored by using TLC. After cooling the mixture to room temperature, a lot of white powder was precipitated from the solution. The powder was filtered and recrystallized in alcohol to obtain white powder as a final product.
  • Dioxane (150.0 mL) was added to a mixture of compound 2-1 (4.00 g, 10.0 mmol, 400.0 g/mol) , compound 2-2 (7.08 g, 21.0 mmol, 337.0 g/mol) , K 3 PO 4 (4.45 g, 21.0 mmol, 212.0 g/mol, 2M in deionized water) , Pd (OAc) 2 (22.0 mg, 0.1 mmol, 224.0 g/mol) , and X-Phos (48.0 mg, 0.1 mmol, 476.0 g/mol) in a two-neck flask under N 2 atmosphere, and then the mixture was stirred under reflux for 12 hrs. The reaction results were monitored by TLC. After cooling the mixture to room temperature, the residue was purified with silica gel and recrystallized to obtain white powder as a final product.
  • n-butyl lithium solution (67.0 mL, 107.2 mmol) in hexane was added dropwise into the flask via an addition funnel for 30 min, and the mixture was further stirred at an internal temperature of -72°C of for 30 min.
  • 2-Isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane (32.0 mL, 171.99 mmol) was added to the resulting dark red solution via an addition funnel for 30 min while maintaining the temperature of below -70°C. After removing a cooling bath, the brown slurry was warmed to room temperature and stirred for 16 hrs.
  • the reactants were concentrated by using a rotary evaporator, dissolved in dichloromethane (350.0 mL) , and washed with water (200.0 mL) to obtain a cloudy mixture.
  • the aqueous layer was extracted with dichloromethane (2 X 150.0 mL) , and the combined organic layers were dried with MgSO 4 , filtered, and concentrated by using a rotary evaporator.
  • the resulting yellow solid was washed with hexane (100.0 mL) and tan colored solids (22.2 g) were obtained by mostly removing the color.
  • the solids were divided into two crops and recrystallized from acetonitrile ( ⁇ 180.0 mL per crop) to obtain pale orange crystalline solids as a title compound (16.5 g, 41.6 mmol, 58%) .
  • the solvent was removed from the mixture, the crude product was dissolved in chloroform and washed with water, the obtained organic layers were concentrated into a small volume followed by loading into a small silica gel plug and removing color and residual boronic ester.
  • the product was loaded into ISCO purification system under anhydrous condition and eluted with gradient of chloroform/hexane to obtain a target compound (9.0 g, 31.0 mmol, 81%) .
  • the reaction mixture was heated at 80°C overnight. Water was added to the solid and the organic matters were extracted with chloroform. The obtained organic layers were dried, the solvent was removed from the layers, and the product was purified via preparative chromatography (ISCO Teledyne purification system) by using a chloroform/EtOAc gradient system to obtain a target compound ( ⁇ 5.5 g, Yield: 87%, Purity by LC: ⁇ 99 %) . The product was recrystallized from boiling chlorobenzene to obtain a target compound (4.5 g, Purity by LC: > 99.8 %) .
  • the reactants were stirred at room temperature overnight.
  • the volatile materials were removed from the reactants by using a rotary evaporator.
  • Anhydrous toluene was added several times to remove trace HCl, and continuously evaporated by using a rotary evaporator.
  • the final product was obtained in the form of colorless to pale yellow powder (28.0 g, 146.4 mmol, 100 %) .
  • the mixture was stirred and cooled to room temperature.
  • the reactants were heated to 100°C in an oil bath for 20 hrs. A complete consumption of 2, 5-dibromoaniline was monitored by TLC.
  • the reactants were poured in warm water (1.5 L) and fine deposits were then formed.
  • the solution was neutralized with sodium carbonate and filtered.
  • the collected residue was dried by suction and rinsed with acetone (25.0 mL) and toluene (25.0 mL) .
  • the filter cake was transported to a 1 L flask, trace water was removed by azeotropic distillation with toluene on a rotary evaporator, and the cake was kept under high-degree vacuum overnight.
  • the dried residue was recrystallized from monochlorobenzene (1.5 L) by using activated carbon as a decolorant.
  • the crystals were separated by filtration and dried under high-degree vacuum (45.05 g, 111.0 mmol, 77.1 %, off-white needles) .
  • Addition purification was effected by recrystallization from 1, 4-dioxane ( ⁇ 0.9 L) .
  • the final product was obtained in the form of off-white crystal (plate) (40.0 g, 98.5 mmol, 68.5%) .
  • the reaction was initiated by the addition of a CuI/N, N’ -dimethylethylenediamine solution, vigorously stirred, and heated to 90°C overnight.
  • the contents of the reaction vessel were added to the diluted aqueous ammonium hydroxide to precipitate the product.
  • the precipitate was separated by filtration, washed with water, rinsed with a small volume of acetone, and dried under high-degree vacuum.
  • the dried precipitate was dissolved in chloroform and filtered through a short plug of silica and basic alumina.
  • the eluted product was collected and the solvent was removed by a rotary evaporator.
  • the residue was dissolved in the minimum quantity of boiling ethyl acetate (approximately 1L) .
  • the crystals were separated by filtration and dried at 45°C under high-degree vacuum overnight.
  • the product was obtained in the form of colorless microcrystal (2.92 g, 5.67 mmol, 69.1 %, Purity by HPLC: 99.8 %) .
  • the mother liquid was completely evaporated, the crystals were re-dissolved in a small volume of toluene, and hexane was added thereto shortly before the precipitation point to obtain a second batch (0.76 g, 1.48 mmol, 18.1 %, Purity by HPLC: 99.6 %) .
  • the product was further purified by sublimation to obtain the purity of the two batches as 99.8 %and 99.7 %, respectively.
  • Comparative Examples 1 and 2 Production of a blue light-emitting OLED device which does not comprise an electron buffer layer according to the present invention
  • OLED devices were produced as follows: A transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an OLED device (GEOMATEC CO., LTD., Japan) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and was then stored in isopropanol. Next, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • ITO indium tin oxide
  • N 4 , N 4’ -diphenyl-N 4 , N 4’ -bis (9-phenyl-9H-carbazol-3-yl) - [1, 1’ -biphenyl] -4, 4’ -diamine (compound HI-1) was introduced into a cell of the vacuum vapor depositing apparatus, and the pressure in the chamber of the apparatus was then controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a first hole injection layer having a thickness of 60 nm on the ITO substrate.
  • Dipyrazino [2, 3-f: 2’ , 3’ -h] quinoxaline-2, 3, 6, 7, 10, 11-hexacarbonitrile (HAT-CN) (compound HI-2) was then introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer.
  • N- ( [1, 1’ -biphenyl] -4-yl) -9, 9-dimethyl-N- (4-(9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluorene-2-amine (compound HT-1) was introduced into another cell of the vacuum vapor depositing apparatus. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a first hole transport layer having a thickness of 20 nm on the second hole injection layer. Compound HT-2 was then introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming a second hole transport layer having a thickness of 5 nm on the first hole transport layer.
  • compound BH-1 as a host was introduced into one cell of the vacuum vapor depositing apparatus and compound BD-1 as a dopant was introduced into another cell.
  • the two materials were evaporated at a different rate and the dopant was deposited in a doping amount of 2 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 20 nm on the second hole transport layer.
  • the current efficiency vs. luminance of the OLED device produced in Comparative Example 1 is depicted in Fig. 3.
  • driving voltage at a luminance of 1,000 nit, luminous efficiency, and CIE color coordinate of the OLED devices produced in the Comparative Examples are as provided in Table 1 below.
  • OLED devices were produced in the same manner as in Comparative Example 1, except that the thickness of the electron transport layer was 30 nm and an electron buffer layer having a thickness of 5 nm was inserted between the light-emitting layer and the electron transport layer.
  • the current efficiency vs. luminance of the OLED device produced in Device Example 2 is depicted in Fig. 3. Also, evaluation results of the devices of Device Examples 1 to 6 are as provided in Table 1 below.
  • Relative electron current property of the devices according to the present invention was compared with the device having no electron buffer layer and not comprising the material of the present invention in the electron buffer layer by preparing an Electron Only Device (EOD) comprising a light-emitting layer.
  • EOD Electron Only Device
  • the device was produced as follows: Barium and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) were introduced into cells in a vacuum vapor depositing apparatus. Thereafter, an electric current was applied to the cells to evaporate the introduced materials, thereby forming a hole blocking layer (HBL) having a thickness of 10 nm on the ITO substrate. Thereafter, compound BH-1 as a host was introduced into one cell and compound BD-1 as a dopant was introduced into another cell of the vacuum vapor depositing apparatus.
  • BCP 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline
  • the two materials were evaporated at a different rate and the dopant was deposited in a doping amount of 2 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 20 nm on a hole transport layer.
  • 2- (4- (9, 10-di (naphthalene-2-yl) anthracene-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole was introduced into one cell and lithium quinolate was introduced into another cell of the vacuum vapor depositing apparatus.
  • the two materials were evaporated at the same rate and were respectively deposited in a doping amount of 50 wt%to form an electron transport layer having a thickness of 35 nm on the light-emitting layer.
  • an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the thickness of the electron transport layer was decreased to 30 nm and an electron buffer layer having a thickness of 5 nm was inserted between the light-emitting layer and the electron transport layer.
  • Voltages at 10 and 100 mA/cm 2 according to each material of the electron buffer layer are provided in Table 2 below.
  • the devices comprising the compounds of the present invention in an electron buffer layer showed similar electron current property to the device having no electron buffer layer.
  • the electron buffer layer of Comparative Example 2 had similar LUMO energy value to the compounds of the present invention, it had poor driving voltage.
  • the organic EL compounds according to the present invention have excellent luminous property compared with conventional materials. Furthermore, a device comprising the organic EL compounds according to the present invention in an electron buffer layer shows excellent luminous property and lowers driving voltage, thereby enhancing power efficiency and improving consumer power.
  • Organic EL Device 101 Substrate
  • Electron Transport Layer 128 Electron Injection Layer
  • Electron Transport Zone 130 Second Electrode

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un dispositif organique EL comprenant un matériau tampon d'électrons, et une première électrode, une seconde électrode opposée à la première électrode, une couche d'émission de lumière disposée entre les deux électrodes, et une zone de transport d'électrons et une couche de tampon d'électrons disposée entre la couche d'émission de lumière et la seconde électrode. En utilisant un matériau tampon d'électrons selon la présente invention, le dispositif organique EL présentant une faible tension de commande et une efficacité lumineuse élevée peut être préparé.
PCT/CN2015/081225 2015-06-11 2015-06-11 Composé organique électroluminescent et dispositif organique électroluminescent le comprenant WO2016197353A1 (fr)

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WO2020009519A1 (fr) * 2018-07-05 2020-01-09 주식회사 엘지화학 Composé polycyclique et diode électroluminescente organique le comprenant
CN110698485A (zh) * 2019-11-21 2020-01-17 北京鼎材科技有限公司 一种化合物及其应用
WO2020199996A1 (fr) * 2019-03-29 2020-10-08 吉林省元合电子材料有限公司 Composé de 1,3,5-triazine substitué, composition et utilisation associées
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CN114773286A (zh) * 2022-05-10 2022-07-22 长春海谱润斯科技股份有限公司 一种含氮杂环有机化合物及其有机发光器件
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JPWO2018008718A1 (ja) * 2016-07-07 2019-04-18 保土谷化学工業株式会社 ベンゾアゾール環構造を有する化合物および有機エレクトロルミネッセンス素子
CN109790132A (zh) * 2016-07-07 2019-05-21 保土谷化学工业株式会社 具有苯并唑环结构的化合物及有机电致发光元件
WO2018008718A1 (fr) * 2016-07-07 2018-01-11 保土谷化学工業株式会社 Composé à structure cyclique de benzazole et élément électroluminescent organique
TWI822672B (zh) * 2017-03-15 2023-11-21 日商保土谷化學工業股份有限公司 有機電致發光元件
WO2019054233A1 (fr) * 2017-09-13 2019-03-21 保土谷化学工業株式会社 Élément électroluminescent organique
US11578065B2 (en) 2017-09-13 2023-02-14 Hodogaya Chemical Co., Ltd. Organic electroluminescence device
CN111095588B (zh) * 2017-09-13 2023-11-17 保土谷化学工业株式会社 有机电致发光元件
CN111095588A (zh) * 2017-09-13 2020-05-01 保土谷化学工业株式会社 有机电致发光元件
JPWO2019054233A1 (ja) * 2017-09-13 2020-08-27 保土谷化学工業株式会社 有機エレクトロルミネッセンス素子
JP7227141B2 (ja) 2017-09-13 2023-02-21 保土谷化学工業株式会社 有機エレクトロルミネッセンス素子
WO2019051976A1 (fr) * 2017-09-18 2019-03-21 深圳市华星光电半导体显示技术有限公司 Dispositif delo et procédé de préparation de matériau liquide à pulvériser sur ce dernier
CN109956933A (zh) * 2017-12-14 2019-07-02 江苏三月光电科技有限公司 一种含有氮杂苯的有机化合物及其在有机电致发光器件上的应用
WO2020009519A1 (fr) * 2018-07-05 2020-01-09 주식회사 엘지화학 Composé polycyclique et diode électroluminescente organique le comprenant
CN112204026A (zh) * 2018-07-05 2021-01-08 株式会社Lg化学 多环化合物及包含其的有机发光二极管
CN112204026B (zh) * 2018-07-05 2024-05-07 株式会社Lg化学 多环化合物及包含其的有机发光二极管
KR102270475B1 (ko) 2018-07-05 2021-06-29 주식회사 엘지화학 다환 화합물 및 이를 포함하는 유기 발광 소자
KR20200005489A (ko) * 2018-07-05 2020-01-15 주식회사 엘지화학 다환 화합물 및 이를 포함하는 유기 발광 소자
CN111747933A (zh) * 2019-03-29 2020-10-09 吉林省元合电子材料有限公司 一种取代的1,3,5-三嗪化合物、组合物及其应用
WO2020199996A1 (fr) * 2019-03-29 2020-10-08 吉林省元合电子材料有限公司 Composé de 1,3,5-triazine substitué, composition et utilisation associées
CN111747933B (zh) * 2019-03-29 2022-03-01 吉林省元合电子材料有限公司 一种取代的1,3,5-三嗪化合物、组合物及其应用
US11758809B2 (en) 2019-09-30 2023-09-12 Shanghai Tianma AM-OLED Co., Ltd. Compound, display panel, and display apparatus
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CN110698485A (zh) * 2019-11-21 2020-01-17 北京鼎材科技有限公司 一种化合物及其应用
CN112979549B (zh) * 2021-02-22 2023-08-29 武汉天马微电子有限公司 一种有机化合物、电致发光材料、oled器件及显示面板
CN112979549A (zh) * 2021-02-22 2021-06-18 上海天马有机发光显示技术有限公司 一种有机化合物、电致发光材料、oled器件及显示面板
CN115340504A (zh) * 2022-05-10 2022-11-15 长春海谱润斯科技股份有限公司 一种含有芴基团的化合物及其有机电致发光器件
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