WO2016064227A1 - Novel organic electroluminescent compounds and an organic electroluminescent device comprising the same - Google Patents

Novel organic electroluminescent compounds and an organic electroluminescent device comprising the same Download PDF

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WO2016064227A1
WO2016064227A1 PCT/KR2015/011220 KR2015011220W WO2016064227A1 WO 2016064227 A1 WO2016064227 A1 WO 2016064227A1 KR 2015011220 W KR2015011220 W KR 2015011220W WO 2016064227 A1 WO2016064227 A1 WO 2016064227A1
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substituted
unsubstituted
organic electroluminescent
alkyl
compound
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Su-Hyun Lee
Hee-Choon Ahn
Young-Mook Lim
Bitnari Kim
Tae-Jin Lee
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Priority to CN201580055365.7A priority Critical patent/CN106795112B/en
Priority to EP15852645.9A priority patent/EP3209643B1/en
Priority to US15/518,276 priority patent/US10633583B2/en
Priority to JP2017519669A priority patent/JP6788581B2/en
Publication of WO2016064227A1 publication Critical patent/WO2016064227A1/en
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Definitions

  • the present disclosure relates to novel organic electroluminescent compounds and an organic electroluminescentdevice comprising the same.
  • An electroluminescent device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • the first organic EL device was developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • An organic EL device is a device changing electrical energy to light by applying electricity to an organic electroluminescent material, and generally has a structure comprising an anode, a cathode, and an organic layer between the anode and the cathode.
  • the organic layer of an organic EL device may be comprised of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (which comprises host and dopant materials), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., and the materials used for the organic layer are categorized by their functions in hole injection material, hole transport material, electron blocking material, light-emitting material, electron buffer material, hole blocking material, electron transport material, electron injection material, etc.
  • the organic EL device due to an application of a voltage, holes are injected from the anode to the light-emitting layer, electrons are injected from the cathode to the light-emitting layer, and excitons of high energies are formed by a recombination of the holes and the electrons.
  • excitons of high energies are formed by a recombination of the holes and the electrons.
  • luminescent organic compounds reach an excited state, and light emission occurs by emitting light from energy due to the excited state of the luminescent organic compounds returning to a ground state.
  • a light-emitting material must have high quantum efficiency, high electron and hole mobility, and the formed light-emitting material layer must be uniform and stable.
  • Light-emitting materials are categorized into blue, green, and red light-emitting materials dependent on the color of the light emission, and additionally yellow or orange light-emitting materials.
  • light-emitting materials can also be categorized into host and dopant materials according to their functions.
  • the host material which acts as a solvent in a solid state and transfers energy, needs to have high purity and a molecular weight appropriate for vacuum deposition. Furthermore, the host material needs to have high glass transition temperature and high thermal degradation temperature to achieve thermal stability, high electro-chemical stability to achieve a long lifespan, ease of forming an amorphous thin film, good adhesion to materials of adjacent layers, and non-migration to other layers.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including (acac)Ir(btp) 2 (bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate)), Ir(ppy) 3 (tris(2-phenylpyridine)iridium) and Firpic (bis(4,6-difluorophenylpyridinato-N,C2)picolinato iridium) as red-, green- and blue-emitting materials, respectively.
  • a light-emitting material can be used as a combination of a host and a dopant to improve color purity, luminous efficiency, and stability. Since host materials greatly influence the efficiency and lifespan of the EL device when using a dopant/host material system as a light-emitting material, their selection is important. At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known as phosphorescent host materials. Recently, Pioneer (Japan) et al., developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III) bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq), etc., as host materials, which were known as hole blocking materials.
  • BCP bathocuproine
  • BAlq aluminum(III) bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • WO 2013/146942 A1 discloses the compounds linked with two carbazoles via arylene group, as a host material.
  • the organic EL devices comprising the compounds recited in the above publication still does not satisfy efficiency, lifespan, etc.
  • the present inventors have tried to find host compounds that can provide superior efficiency and long lifespan compared to the conventional host materials, and have found that the compounds of the present disclosure provide a device with high luminous efficiency and long lifespan.
  • the object of the present disclosure is, firstly, to provide organic electroluminescent compounds having high luminous efficiency, and secondly, to provide an organic electroluminescent device comprising the organic electroluminescent compounds in a light-emitting layer, which is improved long lifespan.
  • Ar 1 represents a substituted or unsubstituted (C6-C30)aryl
  • L represents a substituted or unsubstituted (C6-C30)arylene
  • R 1 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • a represents an integer of 0 to 4; where a represents an integer of 2 or more, each of R 1 may be the same or different.
  • the organic electroluminescent compounds of the present disclosure could provide an organic electroluminescent device having high efficiency and improved lifespan.
  • the present disclosure relates to an organic electroluminescent compound represented by formula 1, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the organic electroluminescent material.
  • Ar 1 represents a substituted or unsubstituted (C6-C15)aryl
  • L represents a substituted or unsubstituted (C6-C15)arylene
  • R 1 represents hydrogen, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C15)aryl.
  • Ar 1 represents (C6-C15)aryl unsubstituted or substituted with a (C1-C10)alkyl, a halogen, a cyano or deuterium;
  • L represents an unsubstituted (C6-C15)arylene;
  • R 1 represents hydrogen, or an unsubstituted (C6-C15)aryl.
  • (C1-C30)alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, 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 constituting the chain, 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 meant to be a linear or branched alkynyl having 2 to 30 carbon atoms
  • 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.
  • the substituents of the substituted alkyl, the substituted alkenyl, the substituted alkynyl, the substituted alkoxy, the substituted cycloalkyl, the substituted aryl(ene), the substituted heteroaryl, the substituted mono- or polycyclic, alicyclic or aromatic ring in the formulas each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30) alkenyl, a (C2-C30) alkynyl, a (C1-C30)
  • the organic electroluminescent compound according to the present disclosure includes the following compounds, but is not limited thereto:
  • organic electroluminescent compound according to the present disclosure can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction scheme 1:
  • Ar 1 , L, R 1 , and a are as defined in formula 1; and Hal represents a halogen.
  • the present disclosure further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the organic electroluminescent material.
  • the organic electroluminescent material can be comprised of the organic electroluminescent compound of the present disclosure alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • the organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes.
  • the organic layer may comprise at least one compound of formula 1.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, an electron buffer layer, and an electron blocking layer.
  • the organic electroluminescent compound of the present disclosure may be comprised in the light-emitting layer.
  • the organic electroluminescent compound of the present disclosure may be comprised as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present disclosure may further comprise one or more compounds other than the compound of formula 1, and may further comprise at least one dopant.
  • organic electroluminescent compound of the present disclosure is comprised as a host material (a first host material) in the light-emitting layer
  • another compounds may be further comprised as a second host material, in which the weight ratio of the first host material to the second host material may be in the range of 1:99 to 99:1.
  • the second host material can be any known phosphorescent host material and preferably, is selected from the group consisting of the compounds of the following formula 2 in view of luminous efficiency.
  • Ma represents a substituted or unsubstituted 5- to 11-membered nitrogen-containing heteroaryl
  • La represents a single bond, or a substituted or unsubstituted (C6-C30)arylene
  • Xa to Xh each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, or a substituted or un
  • the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si, and P.
  • the second host material preferably includes the following:
  • the dopant is preferably at least one phosphorescent dopant.
  • the dopant materials applied to the organic electroluminescent device according to the present disclosure are not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopant is preferably selected from compounds represented by the following formulas 101 to 103.
  • L b is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 , and R 111 to R 123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a cyano, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (C3-C30)cycloalkyl; adjacent substituents of R 106 to R 109 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl; and adjacent substituents of R 120 to R 123 may be linked to each other
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R 124 to R 127 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R 208 to R 211 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
  • r and s each independently represent an integer of 1 to 3; where r or s is an integer of 2 or more, each of R 100 may be the same or different; and
  • e represents an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • a material for preparing an organic electroluminescent device comprises the compound of the present disclosure.
  • the organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes, wherein the organic layer comprises a light-emitting layer, and wherein the light-emitting layer may comprise the material for the organic electroluminescent device of the present disclosure.
  • the organic electroluminescent device of the present disclosure may further comprise, in addition to the compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • the organic layer may further comprise one or more additional light-emitting layers and a charge generating layer.
  • the organic electroluminescent device of the present disclosure may emit white light by further comprising at least one light-emitting layer, which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound of the present disclosure. If necessary, it may further comprise a yellow light-emitting layer or an orange light-emitting layer.
  • a surface layer may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer.
  • a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds
  • the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • N-bromo succinamide N-bromo succinamide
  • EA ethyl acetate
  • An OLED device was produced using the organic electroluminescent compound according to the present disclosure.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • Compound HI-1 was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr.
  • compound HI-2 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer.
  • Compound HT-1 was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer.
  • Compound HT-3 was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer.
  • a light-emitting layer was formed thereon as follows: Compound H-1 was introduced into one cell of said vacuum vapor depositing apparatus as a first host, compound H2-41 was introduced into another cell as a second host, and compound D-96 was introduced into another cell as a dopant.
  • the two host materials were evaporated at the same rate in an amount of 50 wt%, respectively, while the dopant was evaporated at a different rate from the host materials, so that the dopant was deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to coevaporate and form a light-emitting layer having a thickness of 40 nm on the second hole transport layer.
  • Compounds ET-1 and EI-1 were then introduced into two cells of the vacuum vapor depositing apparatus, respectively, and evaporated at a 1:1 rate to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 80 nm was deposited by another vacuum vapor deposition apparatus.
  • an OLED device was produced.
  • the produced OLED device showed a red emission having a luminance of 7,000 cd/m 2 and a luminous efficiency of 27.2 cd/A at 5.1 V.
  • the minimum time for the luminance to decrease to 97% at 5,000 nit was 98 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound HT-2 instead of compound HT-3 as the second hole transport layer, and depositing compound H-1 and compound H2-41 by mixing them in one cell before the deposition, not co-evaporation by introducing them into respective cells.
  • the produced OLED device showed a red emission having a luminance of 7,000 cd/m 2 and a luminous efficiency of 25.8 cd/A at 5.4 V.
  • the minimum time for the luminance to decrease to 97% at 5,000 nit was 113 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-2 as the first host of the light-emitting material.
  • the produced OLED device showed a red emission having a luminance of 7,000 cd/m 2 and a luminous efficiency of 27.4 cd/A at 5.0 V.
  • the minimum time for the luminance to decrease to 97% at 5,000 nit was 76 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-61 as the first host of the light-emitting material.
  • the produced OLED device showed a red emission having a luminance of 7,000 cd/m 2 and a luminous efficiency of 26.5 cd/A at 5.0 V.
  • the minimum time for the luminance to decrease to 97% at 5,000 nit was 41 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-16 as the first host of the light-emitting material.
  • the produced OLED device showed a red emission having a luminance of 7,000 cd/m 2 and a luminous efficiency of 24.7 cd/A at 5.1 V.
  • the minimum time for the luminance to decrease to 97% at 5,000 nit was 101 hours.
  • Comparative Example 1 Preparation of an OLED device using conventional
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound X shown below as the first host of the light-emitting material.
  • the produced OLED device showed a red emission having a luminance of 7000 cd/m 2 and a luminous efficiency of 26.8 cd/A at 5.4 V.
  • the minimum time for the luminance to decrease to 97% at 5,000 nit was 10 hours.
  • An OLED was produced in the same manner as in Device Example 1, except for using compound HT-2 instead of compound HT-3 as the second hole transport layer, using compound Y shown below as the first host of the light-emitting material, and using compound H2-48 instead of compound H2-41 as the second host of the light-emitting material.
  • the produced OLED device showed a red emission having a luminance of 7,000 cd/m 2 and a luminous efficiency of 22.4 cd/A at 5.4 V.
  • the minimum time for the luminance to decrease to 97% at 5,000 nit was 33 hours.
  • the organic electroluminescent compound according to the present disclosure shows the advantages of improved driving lifespan while having equal or greater efficiency compared to conventional devices.
  • the organic electroluminescent compound according to the present disclosure is an advangageous characteristic in recent trends requiring ultra high resolution (UHD) by having long life span and maintaining high luminous efficiency.

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Abstract

The present disclosure relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same. By using the organic electroluminescent compound of the present disclosure, the organic electroluminescent device may improve driving lifespan while maintaining equal or greater efficiency compared to conventional devices.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND AN ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to novel organic electroluminescent compounds and an organic electroluminescentdevice comprising the same.
An electroluminescent device (EL device) is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. The first organic EL device was developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
An organic EL device (OLED) is a device changing electrical energy to light by applying electricity to an organic electroluminescent material, and generally has a structure comprising an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer of an organic EL device may be comprised of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (which comprises host and dopant materials), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., and the materials used for the organic layer are categorized by their functions in hole injection material, hole transport material, electron blocking material, light-emitting material, electron buffer material, hole blocking material, electron transport material, electron injection material, etc. In the organic EL device, due to an application of a voltage, holes are injected from the anode to the light-emitting layer, electrons are injected from the cathode to the light-emitting layer, and excitons of high energies are formed by a recombination of the holes and the electrons. By this energy, luminescent organic compounds reach an excited state, and light emission occurs by emitting light from energy due to the excited state of the luminescent organic compounds returning to a ground state.
The most important factor determining luminous efficiency in an organic EL device is light-emitting materials. A light-emitting material must have high quantum efficiency, high electron and hole mobility, and the formed light-emitting material layer must be uniform and stable. Light-emitting materials are categorized into blue, green, and red light-emitting materials dependent on the color of the light emission, and additionally yellow or orange light-emitting materials. In addition, light-emitting materials can also be categorized into host and dopant materials according to their functions. Recently, the development of an organic EL device providing high efficiency and long lifespan is an urgent issue. In particular, considering EL characteristic requirements for a middle or large-sized panel of OLED, materials showing better characteristics than conventional ones must be urgently developed. The host material, which acts as a solvent in a solid state and transfers energy, needs to have high purity and a molecular weight appropriate for vacuum deposition. Furthermore, the host material needs to have high glass transition temperature and high thermal degradation temperature to achieve thermal stability, high electro-chemical stability to achieve a long lifespan, ease of forming an amorphous thin film, good adhesion to materials of adjacent layers, and non-migration to other layers.
Iridium(III) complexes have been widely known as phosphorescent materials, including (acac)Ir(btp)2 (bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate)), Ir(ppy)3 (tris(2-phenylpyridine)iridium) and Firpic (bis(4,6-difluorophenylpyridinato-N,C2)picolinato iridium) as red-, green- and blue-emitting materials, respectively.
A light-emitting material can be used as a combination of a host and a dopant to improve color purity, luminous efficiency, and stability. Since host materials greatly influence the efficiency and lifespan of the EL device when using a dopant/host material system as a light-emitting material, their selection is important. At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known as phosphorescent host materials. Recently, Pioneer (Japan) et al., developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III) bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq), etc., as host materials, which were known as hole blocking materials.
Although these materials provide good luminous characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of the organic EL device is given by [(π/voltage) × luminous efficiency], and the power efficiency is inversely proportional to the voltage. Although the organic EL device comprising phosphorescent host materials provides higher luminous efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Furthermore, the operational lifespan of the organic EL device is short, and luminous efficiency is still necessary to improve.
Thus, in order to embody excellent properties of the organic EL device, materials constituting the organic layers in the device, in particular host or dopant materials constituting a light-emitting material, should be suitably selected. In this regard, WO 2013/146942 A1 discloses the compounds linked with two carbazoles via arylene group, as a host material. However, the organic EL devices comprising the compounds recited in the above publication still does not satisfy efficiency, lifespan, etc.
In this regard, the present inventors have tried to find host compounds that can provide superior efficiency and long lifespan compared to the conventional host materials, and have found that the compounds of the present disclosure provide a device with high luminous efficiency and long lifespan.
The object of the present disclosure is, firstly, to provide organic electroluminescent compounds having high luminous efficiency, and secondly, to provide an organic electroluminescent device comprising the organic electroluminescent compounds in a light-emitting layer, which is improved long lifespan.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2015011220-appb-I000001
wherein
Ar1 represents a substituted or unsubstituted (C6-C30)aryl;
L represents a substituted or unsubstituted (C6-C30)arylene;
R1 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
a represents an integer of 0 to 4; where a represents an integer of 2 or more, each of R1 may be the same or different.
The organic electroluminescent compounds of the present disclosure could provide an organic electroluminescent device having high efficiency and improved lifespan.
Hereinafter, the present disclosure will be described in detail. However, the following description is intended to explain the disclosure, and is not meant in any way to restrict the scope of the disclosure.
The present disclosure relates to an organic electroluminescent compound represented by formula 1, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the organic electroluminescent material.
In formula 1, preferably, Ar1 represents a substituted or unsubstituted (C6-C15)aryl, L represents a substituted or unsubstituted (C6-C15)arylene, R1 represents hydrogen, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C15)aryl.
In formula 1, more preferably, Ar1 represents (C6-C15)aryl unsubstituted or substituted with a (C1-C10)alkyl, a halogen, a cyano or deuterium; L represents an unsubstituted (C6-C15)arylene; R1 represents hydrogen, or an unsubstituted (C6-C15)aryl.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, 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 constituting the chain, 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 meant to be a linear or branched alkynyl having 2 to 30 carbon atoms constituting the chain, 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 constituting the chain, 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 ring backbone 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.; “5- to 7- membered heterocycloalkyl” is a cycloalkyl having 5 to 7 ring backbone atoms, including at least one heteroatom selected from B, N, O, S, Si, and P, preferably O, S, and N, and includes pyrrolidine, thiolan, tetrahydropyran, etc.; “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 ring backbone 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.; “3- to 30-membered heteroaryl(ene)” is an aryl having 3 to 30 ring backbone atoms, preferably 3 to 20 ring backbone atoms, and more preferably 3 to 15 ring backbone atoms, including at least one, preferably 1 to 4 heteroatoms selected from the group consisting of B, N, O, S, Si, and P; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Further, “halogen” includes F, Cl, Br, and I.
Herein, “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. The substituents of the substituted alkyl, the substituted alkenyl, the substituted alkynyl, the substituted alkoxy, the substituted cycloalkyl, the substituted aryl(ene), the substituted heteroaryl, the substituted mono- or polycyclic, alicyclic or aromatic ring in the formulas each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30) alkenyl, a (C2-C30) alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a 3- to 7-membered heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a 3- to 30-membered heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a 3- to 30-membered heteroaryl, a cyano or (C1-C30)alkyl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di- (C1-C30)alkylamino, a mono- or di- (C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl.
The organic electroluminescent compound according to the present disclosure includes the following compounds, but is not limited thereto:
Figure PCTKR2015011220-appb-I000002
Figure PCTKR2015011220-appb-I000003
Figure PCTKR2015011220-appb-I000004
Figure PCTKR2015011220-appb-I000005
Figure PCTKR2015011220-appb-I000006
Figure PCTKR2015011220-appb-I000007
Figure PCTKR2015011220-appb-I000008
Figure PCTKR2015011220-appb-I000009
The organic electroluminescent compound according to the present disclosure can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction scheme 1:
Reaction scheme 1
Figure PCTKR2015011220-appb-I000010
Reaction scheme 2
Figure PCTKR2015011220-appb-I000011
Reaction scheme 3
Figure PCTKR2015011220-appb-I000012
wherein
Ar1, L, R1, and a are as defined in formula 1; and Hal represents a halogen.
The present disclosure further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the organic electroluminescent material. The organic electroluminescent material can be comprised of the organic electroluminescent compound of the present disclosure alone, or can further include conventional materials generally used in organic electroluminescent materials.
The organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes. The organic layer may comprise at least one compound of formula 1.
One of the first and second electrodes may be an anode, and the other may be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, an electron buffer layer, and an electron blocking layer.
The organic electroluminescent compound of the present disclosure may be comprised in the light-emitting layer. When used in the light-emitting layer, the organic electroluminescent compound of the present disclosure may be comprised as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present disclosure may further comprise one or more compounds other than the compound of formula 1, and may further comprise at least one dopant.
When the organic electroluminescent compound of the present disclosure is comprised as a host material (a first host material) in the light-emitting layer, another compounds may be further comprised as a second host material, in which the weight ratio of the first host material to the second host material may be in the range of 1:99 to 99:1.
The second host material can be any known phosphorescent host material and preferably, is selected from the group consisting of the compounds of the following formula 2 in view of luminous efficiency.
Figure PCTKR2015011220-appb-I000013
wherein
Ma represents a substituted or unsubstituted 5- to 11-membered nitrogen-containing heteroaryl;
La represents a single bond, or a substituted or unsubstituted (C6-C30)arylene;
Xa to Xh each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, or a substituted or unsubstituted mono- or di- (C6-C30)arylamino; or are linked to each other to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and
the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si, and P.
Specifically, the second host material preferably includes the following:
Figure PCTKR2015011220-appb-I000014
Figure PCTKR2015011220-appb-I000015
Figure PCTKR2015011220-appb-I000016
Figure PCTKR2015011220-appb-I000017
Figure PCTKR2015011220-appb-I000018
Figure PCTKR2015011220-appb-I000019
Figure PCTKR2015011220-appb-I000020
Figure PCTKR2015011220-appb-I000021
Figure PCTKR2015011220-appb-I000022
Figure PCTKR2015011220-appb-I000023
Figure PCTKR2015011220-appb-I000024
Figure PCTKR2015011220-appb-I000025
Figure PCTKR2015011220-appb-I000026
Figure PCTKR2015011220-appb-I000027
Figure PCTKR2015011220-appb-I000028
Figure PCTKR2015011220-appb-I000029
Figure PCTKR2015011220-appb-I000030
Figure PCTKR2015011220-appb-I000031
Figure PCTKR2015011220-appb-I000032
Figure PCTKR2015011220-appb-I000033
Figure PCTKR2015011220-appb-I000034
Figure PCTKR2015011220-appb-I000035
Figure PCTKR2015011220-appb-I000036
Figure PCTKR2015011220-appb-I000037
Figure PCTKR2015011220-appb-I000038
Figure PCTKR2015011220-appb-I000039
Figure PCTKR2015011220-appb-I000040
Figure PCTKR2015011220-appb-I000041
Figure PCTKR2015011220-appb-I000042
Figure PCTKR2015011220-appb-I000043
Figure PCTKR2015011220-appb-I000044
Figure PCTKR2015011220-appb-I000045
Figure PCTKR2015011220-appb-I000046
Figure PCTKR2015011220-appb-I000047
Figure PCTKR2015011220-appb-I000048
Figure PCTKR2015011220-appb-I000049
Figure PCTKR2015011220-appb-I000050
Figure PCTKR2015011220-appb-I000051
Figure PCTKR2015011220-appb-I000052
Figure PCTKR2015011220-appb-I000053
Figure PCTKR2015011220-appb-I000054
Figure PCTKR2015011220-appb-I000055
Figure PCTKR2015011220-appb-I000056
Figure PCTKR2015011220-appb-I000057
Figure PCTKR2015011220-appb-I000058
Figure PCTKR2015011220-appb-I000059
Figure PCTKR2015011220-appb-I000060
Figure PCTKR2015011220-appb-I000061
Figure PCTKR2015011220-appb-I000062
Figure PCTKR2015011220-appb-I000063
Figure PCTKR2015011220-appb-I000064
Figure PCTKR2015011220-appb-I000065
Figure PCTKR2015011220-appb-I000066
Figure PCTKR2015011220-appb-I000067
Figure PCTKR2015011220-appb-I000068
Figure PCTKR2015011220-appb-I000069
Figure PCTKR2015011220-appb-I000070
Figure PCTKR2015011220-appb-I000071
Figure PCTKR2015011220-appb-I000072
Figure PCTKR2015011220-appb-I000073
Figure PCTKR2015011220-appb-I000074
Figure PCTKR2015011220-appb-I000075
The dopant is preferably at least one phosphorescent dopant. The dopant materials applied to the organic electroluminescent device according to the present disclosure are not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopant is preferably selected from compounds represented by the following formulas 101 to 103.
Figure PCTKR2015011220-appb-I000076
Figure PCTKR2015011220-appb-I000077
wherein Lb is selected from the following structures:
Figure PCTKR2015011220-appb-I000078
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
R101 to R109, and R111 to R123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a cyano, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (C3-C30)cycloalkyl; adjacent substituents of R106 to R109 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl; and adjacent substituents of R120 to R123 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., quinoline unsubstituted or substituted with alkyl or aryl;
R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R124 to R127 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R208 to R211 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
r and s each independently represent an integer of 1 to 3; where r or s is an integer of 2 or more, each of R100 may be the same or different; and
e represents an integer of 1 to 3.
Specifically, the phosphorescent dopant materials include the following:
Figure PCTKR2015011220-appb-I000079
Figure PCTKR2015011220-appb-I000080
Figure PCTKR2015011220-appb-I000081
Figure PCTKR2015011220-appb-I000082
Figure PCTKR2015011220-appb-I000083
Figure PCTKR2015011220-appb-I000084
Figure PCTKR2015011220-appb-I000085
Figure PCTKR2015011220-appb-I000086
Figure PCTKR2015011220-appb-I000087
Figure PCTKR2015011220-appb-I000088
Figure PCTKR2015011220-appb-I000089
Figure PCTKR2015011220-appb-I000090
Figure PCTKR2015011220-appb-I000091
Figure PCTKR2015011220-appb-I000092
Figure PCTKR2015011220-appb-I000093
Figure PCTKR2015011220-appb-I000094
Figure PCTKR2015011220-appb-I000095
Figure PCTKR2015011220-appb-I000096
Figure PCTKR2015011220-appb-I000097
Figure PCTKR2015011220-appb-I000098
Figure PCTKR2015011220-appb-I000099
Figure PCTKR2015011220-appb-I000100
Figure PCTKR2015011220-appb-I000101
Figure PCTKR2015011220-appb-I000102
Figure PCTKR2015011220-appb-I000103
According to an additional aspect of the present disclosure, a material for preparing an organic electroluminescent device is provided. The material comprises the compound of the present disclosure.
The organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes, wherein the organic layer comprises a light-emitting layer, and wherein the light-emitting layer may comprise the material for the organic electroluminescent device of the present disclosure.
The organic electroluminescent device of the present disclosure may further comprise, in addition to the compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present disclosure, the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal. The organic layer may further comprise one or more additional light-emitting layers and a charge generating layer.
In addition, the organic electroluminescent device of the present disclosure may emit white light by further comprising at least one light-emitting layer, which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound of the present disclosure. If necessary, it may further comprise a yellow light-emitting layer or an orange light-emitting layer.
In the organic electroluminescent device of the present disclosure, preferably, at least one layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device of the present disclosure, a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds, and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present disclosure, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the compound of the present disclosure, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound H-1
Figure PCTKR2015011220-appb-I000104
Figure PCTKR2015011220-appb-I000105
Figure PCTKR2015011220-appb-I000106
Preparation of compound 1-1
After introducing (9-phenyl-9H-carbazole-3-yl) boronic acid 30 g (104.49 mmol), 1-bromo-4-iodobenzene 30 g (104.49 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) 3.6 g (3.13 mmol), sodium carbonate 28 g (261.23 mmol), toluene 520 mL and ethanol 130 mL into a reaction vessel, distilled water 130 mL was added thereto, and the mixture was then stirred under reflux for 4 hours at 120 °C. After completing the reaction, the mixture was washed with distilled water and extracted with ethyl acetate (EA). The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom using a rotary evaporator, and the remaining product was purified by column chromatography to obtain compound 1-1 27 g (65%).
Preparation of compound 1-2
After introducing carbazole 20 g (120 mmol), 2-bromonaphthalene 30 g (143 mmol), copper(I) iodide (CuI) 11.7 g (59.81 mmol), ethylenediamine (EDA) 8 mL (120 mmol), NaOt-Bu 64 g (299 mmol) and toluene 600 mL into a reaction vessel, the mixture was then stirred under reflux for 8 hours at 120 °C. After completing the reaction, the mixture was washed with distilled water and extracted with ethyl acetate (EA). The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom using a rotary evaporator, and the remaining product was purified by column chromatography to obtain compound 1-2 13 g (37%).
Preparation of compound 1-3
After dissolving compound 1-2 13 g (44 mmol) in dimethylformamide (DMF) into a reaction vessel, N-bromo succinamide (NBS) was dissolved in dimethylformamide and introduced into the reaction mixture. After stirring the mixture for 4 hours at room temperature, the mixture was washed with distilled water and extracted with ethyl acetate (EA). The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom using a rotary evaporator, and the remaining product was purified by column chromatography to obtain compound 1-3 14 g (83%).
Preparation of compound 1-4
After introducing compound 1-3 14 g (36 mmol), bis(pinacolato)diboran 11 g (44 mmol), bis(triphenylphosphine)palladium(II)dichloride (PdCl2(PPh3)2) 1.3 g (2 mmol), potassium acetate (KOAc) 9 g (91 mmol) and 1,4-dioxane 180 mL into a reaction vessel, the mixture was then stirred under reflux for 2 hours at 140 °C. After completing the reaction, the mixture was washed with distilled water and extracted with ethyl acetate (EA). The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom using a rotary evaporator, and the remaining product was purified by column chromatography to obtain compound 1-4 8 g (52%).
Preparation of compound H-1
After introducing compound 1-1 7 g (17 mmol), compound 1-4 8 g (19 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) 0.6 g (0.5 mmol), sodium carbonate 4.5 g (43 mmol), toluene 100 mL and ethanol 25 mL into a reaction vessel, distilled water 25 mL was added thereto, and the mixture was then stirred under reflux for 4 hours at 120 °C. After completing the reaction, the mixture was washed with distilled water and extracted with ethyl acetate (EA). The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom using a rotary evaporator, and the remaining product was purified by column chromatography to obtain compound H-1 4 g (37%).
Figure PCTKR2015011220-appb-I000107
Example 2: Preparation of compound H-2
Figure PCTKR2015011220-appb-I000108
Preparation of compound 2-1
After introducing 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 30 g (102.3 mmol), 1-bromo-4-iodobenzene 13.2 g (46.5 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) 2.7 g (2.3 mmol), K2CO3 32.1 g (232 mmol), toluene 300 mL, EtOH 100 mL and H2O 100 mL into a flask, the mixture was then stirred. After stirring under reflux for 6 hours, the mixture was cooled to room temperature and extracted with EA and distilled water. The obtained organic layer was distilled under reduced pressure, and the remaining product was purified by column chromatography to obtain compound 2-1 18 g (91%).
Preparation of compound H-2
After introducing compound 2-1 18 g (44.1 mmol), 2-bromonaphthalene 27.4 g (132.2 mmol), palladium (II) acetate (Pd(OAc)2) 1.0 g (4.4 mmol), 50% tri-tert-butylphosphine (P(t-Bu)3) 4.3 mL (8.8 mmol), NaOt-Bu 21 g (220.3 mmol) and toluene 600 mL into a flask, the mixture was then stirred under reflux for 3 hours. The mixture was cooled to room temperature and extracted with EA and distilled water. The obtained organic layer was distilled under reduced pressure, and the remaining product was purified by column chromatography to obtain compound H-2 5.8 g (20%).
Figure PCTKR2015011220-appb-I000109
Example 3: Preparation of compound H-16
Figure PCTKR2015011220-appb-I000110
Preparation of compound 3-1
After dissolving (9-phenyl-9H-carbazole-2-yl) boronic acid 13.5 g (46.9 mmol), 1-bromo-4-iodobenzene 26.5 g (93.8 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) 2.7 g (2.35 mmol), potassium carbonate (K2CO3) 16.2 g (117.3 mmol), toluene 180 mL, EtOH 30 mL and H2O 60 mL into a flask, the mixture was then under reflux for 5 hours at 120 °C. After completing the reaction, the mixture was filtered under reduced pressure with methylene chloride (MC) and was purified by column chromatography. The solid produced by introducing a methanol was filtered under reduced pressure to obtain compound 3-1 14.0 g (75%).
Preparation of compound 3-2
After dissolving compound 3-1 14.0 g (35.2 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 9.4 g (31.9 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) 1.84 g (1.6 mmol), potassium carbonate (K2CO3) 11 g (79.8 mmol), toluene 120 mL, EtOH 20 mL and H2O 40 mL into a flask, the mixture was then under reflux for 4 hours at 120 °C. After completing the reaction, the mixture was filtered under reduced pressure with methylene chloride (MC) and was purified by column chromatography. The solid produced by introducing a methanol was filtered under reduced pressure to obtain compound 3-2 9.2 g (60%).
Preparation of compound H-16
After dissolving compound 3-2 9.14 g (18.9 mmol), 2-iodonaphthalene 5.9 g (28.3 mmol), CuI 1.8 g (9.43 mmol), ethylenediamine (EDA) 1.27 mL (18.86 mmol), K3PO4 10.0 g (47.2 mmol) and o-xylene 95 mL into a flask, the mixture was then under reflux for 5 hours at 150 °C. After completing the reaction, the mixture was filtered under reduced pressure with methylene chloride (MC) and was purified by column chromatography. The solid produced by introducing a methanol was filtered under reduced pressure to obtain compound H-16 10.5 g (91%).
Figure PCTKR2015011220-appb-I000111
Example 4: Preparation of compound H-61
Figure PCTKR2015011220-appb-I000112
Preparation of compound 4-1
After dissolving 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 30 g (102.30 mmol), 1,3-dibromobenzene 6.4 mL (51.20 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) 7.10 g (6.14 mmol), potassium carbonate (K2CO3) 70.7 g (511.50 mmol), toluene 512 mL, EtOH 128 mL and H2O 128 mL into a flask, the mixture was then under reflux for 2 days at 120 °C. After completing the reaction, the obtained organic layer was extracted with ethyl acetate and concentrated, and the remaining product was washed with MeOH to obtain compound 4-1 15.2 g (73%).
Preparation of compound H-61
After dissolving compound 4-1 21 g (51.20 mmol), 2-bromonaphthalene 27 g (127.9 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) 2.4 g (2.56 mmol), P(t-Bu)3 2.5 mL (5.12 mmol) and NaOt-Bu 15 g (153.6 mmol) in toluene 256 mL, the mixture was then under reflux for 5 hours. After completing the reaction, the remaining product was purified by column chromatography to obtain compound H-61 8.7 g (26%).
Figure PCTKR2015011220-appb-I000113
Device Example 1: Preparation of an OLED device using the organic
electroluminescent compounds of the present disclosure
An OLED device was produced using the organic electroluminescent compound according to the present disclosure. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. Compound HI-1 was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a first hole injection layer having a thickness of 80 nm on the ITO substrate. Next, compound HI-2 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer. Compound HT-1 was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer. Compound HT-3 was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer. After forming the hole injection layer and the hole transport layer, a light-emitting layer was formed thereon as follows: Compound H-1 was introduced into one cell of said vacuum vapor depositing apparatus as a first host, compound H2-41 was introduced into another cell as a second host, and compound D-96 was introduced into another cell as a dopant. The two host materials were evaporated at the same rate in an amount of 50 wt%, respectively, while the dopant was evaporated at a different rate from the host materials, so that the dopant was deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to coevaporate and form a light-emitting layer having a thickness of 40 nm on the second hole transport layer. Compounds ET-1 and EI-1 were then introduced into two cells of the vacuum vapor depositing apparatus, respectively, and evaporated at a 1:1 rate to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. After depositing compound EI-1 as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 80 nm was deposited by another vacuum vapor deposition apparatus. Thus, an OLED device was produced.
Figure PCTKR2015011220-appb-I000114
The produced OLED device showed a red emission having a luminance of 7,000 cd/m2 and a luminous efficiency of 27.2 cd/A at 5.1 V. The minimum time for the luminance to decrease to 97% at 5,000 nit was 98 hours.
Device Example 2: Preparation of an OLED device using the organic
electroluminescent compounds of the present disclosure
An OLED device was produced in the same manner as in Device Example 1, except for using compound HT-2 instead of compound HT-3 as the second hole transport layer, and depositing compound H-1 and compound H2-41 by mixing them in one cell before the deposition, not co-evaporation by introducing them into respective cells.
The produced OLED device showed a red emission having a luminance of 7,000 cd/m2 and a luminous efficiency of 25.8 cd/A at 5.4 V. The minimum time for the luminance to decrease to 97% at 5,000 nit was 113 hours.
Device Example 3: Preparation of an OLED device using the organic
electroluminescent compounds of the present disclosure
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-2 as the first host of the light-emitting material.
The produced OLED device showed a red emission having a luminance of 7,000 cd/m2 and a luminous efficiency of 27.4 cd/A at 5.0 V. The minimum time for the luminance to decrease to 97% at 5,000 nit was 76 hours.
Device Example 4: Preparation of an OLED device using the organic
electroluminescent compounds of the present disclosure
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-61 as the first host of the light-emitting material.
The produced OLED device showed a red emission having a luminance of 7,000 cd/m2 and a luminous efficiency of 26.5 cd/A at 5.0 V. The minimum time for the luminance to decrease to 97% at 5,000 nit was 41 hours.
Device Example 5: Preparation of an OLED device using the organic
electroluminescent compounds of the present disclosure
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-16 as the first host of the light-emitting material.
The produced OLED device showed a red emission having a luminance of 7,000 cd/m2 and a luminous efficiency of 24.7 cd/A at 5.1 V. The minimum time for the luminance to decrease to 97% at 5,000 nit was 101 hours.
Comparative Example 1: Preparation of an OLED device using conventional
organic electroluminescent compounds
An OLED device was produced in the same manner as in Device Example 1, except for using compound X shown below as the first host of the light-emitting material.
The produced OLED device showed a red emission having a luminance of 7000 cd/m2 and a luminous efficiency of 26.8 cd/A at 5.4 V. The minimum time for the luminance to decrease to 97% at 5,000 nit was 10 hours.
Figure PCTKR2015011220-appb-I000115
Comparative Example 2: Preparation of an OLED device using conventional
organic electroluminescent compounds
An OLED was produced in the same manner as in Device Example 1, except for using compound HT-2 instead of compound HT-3 as the second hole transport layer, using compound Y shown below as the first host of the light-emitting material, and using compound H2-48 instead of compound H2-41 as the second host of the light-emitting material.
The produced OLED device showed a red emission having a luminance of 7,000 cd/m2 and a luminous efficiency of 22.4 cd/A at 5.4 V. The minimum time for the luminance to decrease to 97% at 5,000 nit was 33 hours.
Figure PCTKR2015011220-appb-I000116
The organic electroluminescent compound according to the present disclosure shows the advantages of improved driving lifespan while having equal or greater efficiency compared to conventional devices. Particularly, the organic electroluminescent compound according to the present disclosure is an advangageous characteristic in recent trends requiring ultra high resolution (UHD) by having long life span and maintaining high luminous efficiency.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2015011220-appb-I000117
    wherein
    Ar1 represents a substituted or unsubstituted (C6-C30)aryl;
    L represents a substituted or unsubstituted (C6-C30)arylene;
    R1 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
    a represents an integer of 0 to 4; where a represents an integer of 2 or more, each of R1 may be the same or different.
  2. The organic electroluminescent compound according to claim 1, wherein Ar1 represents a substituted or unsubstituted (C6-C15)aryl; L represents a substituted or unsubstituted (C6-C15)arylene; R1 represents hydrogen, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C15)aryl.
  3. The organic electroluminescent compound according to claim 1, wherein Ar1 represents (C6-C15)aryl unsubstituted or substituted with a (C1-C10)alkyl, a halogen, a cyano or deuterium; L represents an unsubstituted (C6-C15)arylene; R1 represents hydrogen, or an unsubstituted (C6-C15)aryl.
  4. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted alkyl or the substituted aryl(ene), each independently, are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7-membered)heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (3- to 30-membered)heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di-(C1-C30)alkylamino, a mono- or di-(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl and a (C1-C30)alkyl(C6-C30)aryl.
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2015011220-appb-I000118
    Figure PCTKR2015011220-appb-I000119
    Figure PCTKR2015011220-appb-I000120
    Figure PCTKR2015011220-appb-I000121
    Figure PCTKR2015011220-appb-I000122
    Figure PCTKR2015011220-appb-I000123
    Figure PCTKR2015011220-appb-I000124
    Figure PCTKR2015011220-appb-I000125
  6. An organic electroluminescent device comprising the compound according to claim 1.
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