WO2014200244A1 - Novel organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

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

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WO2014200244A1
WO2014200244A1 PCT/KR2014/005082 KR2014005082W WO2014200244A1 WO 2014200244 A1 WO2014200244 A1 WO 2014200244A1 KR 2014005082 W KR2014005082 W KR 2014005082W WO 2014200244 A1 WO2014200244 A1 WO 2014200244A1
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group
substituted
unsubstituted
organic electroluminescent
alkyl
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PCT/KR2014/005082
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French (fr)
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Mi-Ja Lee
Nam-Kyun Kim
Chi-Sik Kim
Young-Jun Cho
Kyung-Joo Lee
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority to CN201480030900.9A priority Critical patent/CN105246898A/en
Publication of WO2014200244A1 publication Critical patent/WO2014200244A1/en

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Definitions

  • the present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer [see Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor for determining luminescent efficiency of an organic EL device is a light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • developing phosphorescent materials is one of the best methods to theoretically enhance luminescent efficiency by four (4) times compared to fluorescent materials.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinatoiridium (Firpic) as red, green and blue materials, respectively.
  • a mixed system of a dopant/host material can be used as a light-emitting material to improve color purity, luminescent efficiency and stability. If the dopant/host material system is used, the selection of the host material is important because the host material greatly influences on efficiency and performance of a light-emitting device. In conventional technique, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known as a phosphorescent host material.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • CuPc copper phthalocyanine
  • NPB 4,4’-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • TPD N,N’-diphenyl-N,N’-bis(3-methylphenyl)-(1,1’-biphenyl)-4,4’-diamine
  • MTDATA 4,4’,4”-tris(3-methylphenylphenylamino)triphenylamine
  • the organic EL device comprising the materials has low quantum efficiency and a short operating lifespan, because, when the organic EL device is driven at a high current, thermal stress is generated between an anode and a hole injection layer, thereby rapidly reducing the operating lifespan of the device. Furthermore, movement of holes is great in organic materials used in a hole injection layer, and thus the hole-electron charge balance is broken and quantum efficiency (cd/A) is reduced.
  • Japanese Patent Application Laid-open No. 2000-077186 discloses fused dibenzofuran-based ring compounds as compounds used in a light-emitting layer of an organic EL device.
  • the organic EL device comprising the compounds has high driving voltage and low light-emitting luminance versus driving voltage.
  • the present inventors have found that by using phosphorescent host compounds having excellent electron transport efficiency in a light-emitting layer of an organic EL device, the hole-electron charge balance is well established in a light-emitting layer, the driving voltage of the device is reduced, and the power efficiency of the device is enhanced. Furthermore, an organic EL device comprising the host material does not need to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.
  • the objective of the present invention is to provide an organic electroluminescent compound having high current transport efficiency, and an organic electroluminescent device having low driving voltage and enhanced power efficiency by comprising the organic electroluminescent compound in a light-emitting layer.
  • X 1 and X 2 each independently represent CR 1 R 2 , NR 9 , O or S;
  • Y 1 to Y 12 each independently represent CR 3 or N;
  • R 1 and R 2 each independently represent hydrogen, a substituted or unsubstituted (C6-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
  • R 3 represents hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl group, -NR 4 R 5 , -SiR 6 R 7 R 8 , a cyano group, a nitro group, or a hydroxyl group;
  • R 4 to R 9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono- or polycyclic, (C5-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 organic electroluminescent compound according to the present invention improves the current property of an organic electroluminescent device thereby reducing the driving voltage of the device, and has the advantages of providing an organic EL device having advanced power efficiency. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not need to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.
  • the present invention relates to an organic electroluminescent compound represented by formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the material.
  • X 1 and X 2 each independently represent CR 1 R 2 or NR 9 ; Y 1 to Y 12 each independently represent CR 3 ; R 1 to R 3 each independently represent hydrogen, a substituted or unsubstituted (C1-C10)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 20-membered heteroaryl group, -SiR 6 R 7 R 8 , a substituted or unsubstituted (C3-C30)cycloalkyl group, or a cyano group; and R 4 to R 9 each independently represent a substituted or unsubstituted (C1-C6)alkyl group, a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 20-membered heteroaryl group.
  • R 1 and R 2 each independently represent an unsubstituted (C1-C10)alkyl group or an unsubstituted (C6-C15)aryl group
  • R 6 to R 8 each independently represent an unsubstituted (C1-C6)alkyl group or an unsubstituted (C6-C15)aryl group
  • R 9 represents a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group.
  • (C1-C30)alkyl is meant to be a linear or branched alkyl(ene) 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, iso-propoxy, 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 cycloalkyl group, the substituted aryl group, the substituted heteroaryl group, the substituted heterocycloalkyl group, and the substituted mono- or polycyclic (C5-C30) alicyclic or aromatic ring in R 1 to R 9 of formula 1 each independently are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl group which is unsubstituted or substituted with halogen(s); a (C1-C30)alkoxy group; a (C6-C30)aryl group; a 5- to 30-membered heteroaryl group which is unsubstituted or substituted with a (
  • organic electroluminescent compounds according to the present invention include the following compounds, but are not limited thereto:
  • organic electroluminescent compounds according to the present invention 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:
  • the present invention further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the material can be comprised of the organic electroluminescent compound of the present invention alone, or can further include conventional materials generally included in organic electroluminescent materials.
  • the organic electroluminescent device may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one organic electroluminescent compound of formula 1.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, and an electron blocking layer.
  • the light-emitting layers can include the organic electroluminescent compound of the present invention.
  • the organic electroluminescent compounds of the present invention can be included as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present invention may further comprise at least one other compounds as host materials, in addition to the organic electroluminescent compound of the present invention, and may further include at least one dopant.
  • the organic electroluminescent compound of the present invention is included as the host material (a first host material) in the light-emitting layer, other compounds may be included as a second host material.
  • the first host material and the second host material may be in the range of 1:99 to 99:1 in a weight ratio.
  • the second host material which is other compounds in addition to the organic electroluminescent compound of the present invention, can be any of the known phosphorescent hosts and preferably, is selected from the group consisting of the compounds of the following formulae 2 to 6 in view of luminescent efficiency:
  • X represents -O- or -S-;
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- or 30-membered heteroaryl group, or R 25 R 26 R 27 Si-; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- or 30-membered heteroarylene group;
  • M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group;
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )- or -C(R 32 )(R 33 )-; and Y 1 and Y 2 are not simultaneously present;
  • R 31 to R 33 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-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 R 32 and R 33 may be the same or different;
  • h and i each independently represent an integer of 1 to 3;
  • j, k, l and m each independently represent an integer of 0 to 4.
  • each (Cz-L 4 ), each (Cz), each R 21 , each R 22 , each R 23 or each R 24 is the same or different.
  • the second host material includes the following:
  • TPS represents triphenylsilyl
  • the dopants contained in the organic electroluminescent device of the present invention are preferably one or more phosphorescent dopants.
  • the phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not specifically limited, but preferably may be selected from complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably 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 may be selected from the group consisting of the compounds represented by the following formulae 7 to 9:
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group
  • R 101 to R 109 and R 111 to R 123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, a cyano group, or a substituted or unsubstituted (C1-C30)alkoxy group
  • R 120 to R 123 are linked to an adjacent substituent(s) to form a fused ring, for example, quinoline
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or
  • the phosphorescent dopant material includes the following:
  • the present invention further provides the composition for the organic electroluminescent device.
  • the composition comprises the compounds of the present invention as a host material.
  • the organic electroluminescent device of the present invention comprises a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises a light-emitting layer and the light-emitting layer may comprise the composition for the organic electroluminescent device of the present invention.
  • the organic electroluminescent device of the present invention comprises the organic electroluminescent compounds of formula 1 and may further include 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 organic electroluminescent compounds 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 d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • the organic layer may further comprise a light-emitting layer and a charge-generating layer.
  • the organic electroluminescent device of the present invention 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, besides the organic electroluminescent compound of the present invention; and may further include a yellow or orange light-emitting layer, if necessary.
  • a surface layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s).
  • a chalcogenide (includes oxides) layer of silicon or aluminum is placed on an anode surface of a light-emitting medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer.
  • the surface layer provides operating stability for the organic electroluminescent device.
  • 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 an 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 a light-emitting 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 a light-emitting medium.
  • 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 organic electroluminescent device having two or more light-emitting layers and emitting white light.
  • dry film-forming methods such as vacuum deposition, sputtering, plasma, ion plating methods, etc.
  • wet film-forming methods such as spin coating, dip coating, flow coating methods, etc.
  • a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • suitable solvents such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
  • An organic light-emitting diode (OLED) device comprising the organic electroluminescent compound according to the present invention was produced as follows: A transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an OLED device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • ITO indium tin oxide
  • N 1 ,N 1’ -([1,1’-biphenyl]-4,4’-diyl)bis(N 1 -(naphthalene-1-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine) was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was 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 hole transport layer having a thickness of 20 nm on the hole injection layer.
  • Compound H-6 was introduced as a host into one cell of the vacuum vapor depositing apparatus, and compound D-87 as a dopant was introduced into another cell.
  • the two materials were evaporated at different rates and the dopant was deposited in a doping amount of 4 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidiazole was introduced into one cell, and lithium quinolate was introduced into another cell.
  • the two materials were evaporated at the same rates and were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the produced OLED device showed red emission having a luminance of 1000 cd/m 2 at 3.4 V. Furthermore, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 80 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except that compound H-7 was used as a host and compound D-88 was used as a dopant in a light-emitting material.
  • the produced OLED device showed red emission having a luminance of 1000 cd/m 2 at 3.6 V. Furthermore, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 40 hours.
  • Comparative Example 1 Production of an OLED device by using
  • An OLED device was produced in the same manner as in Device Example 1, except that compound E-1 was used as a host and compound D-11 was used as a dopant in a light-emitting material.
  • the produced OLED device showed red emission having a luminance of 1000 cd/m 2 at 4.0 V. Furthermore, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 20 hours.
  • the organic electroluminescent compound according to the present invention reduces the driving voltage of an organic electroluminescent device by improving the current property of the device. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not need to comprise a hole blocking layer and improves lifespan.

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present invention improves the current property of the device thereby reducing the driving voltage of the device. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not need to comprise a hole blocking layer and has an improved lifespan.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer [see Appl. Phys. Lett. 51, 913, 1987].
The most important factor for determining luminescent efficiency of an organic EL device is a light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, developing phosphorescent materials is one of the best methods to theoretically enhance luminescent efficiency by four (4) times compared to fluorescent materials. Until now, Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinatoiridium (Firpic) as red, green and blue materials, respectively.
A mixed system of a dopant/host material can be used as a light-emitting material to improve color purity, luminescent efficiency and stability. If the dopant/host material system is used, the selection of the host material is important because the host material greatly influences on efficiency and performance of a light-emitting device. In conventional technique, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known as a phosphorescent host material. Pioneer (Japan) et al., currently developed a high performance organic EL device by employing bathocuproine (BCP), aluminum(III) bis(2-methyl-8-quinolinato)(4-phenylphenolate) (BAlq), etc., which were used in a hole blocking layer, as host materials.
Although these phosphorescent host materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperatures and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to voltage. An organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) and has a higher driving voltage than one comprising fluorescent host materials. Thus, the organic EL device using conventional phosphorescent materials has no advantage in terms of power efficiency (lm/W). (3) Furthermore, the operating lifespan and luminous efficiency of the organic EL device are not satisfactory.
Meanwhile, copper phthalocyanine (CuPc), 4,4’-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N’-diphenyl-N,N’-bis(3-methylphenyl)-(1,1’-biphenyl)-4,4’-diamine (TPD), 4,4’,4”-tris(3-methylphenylphenylamino)triphenylamine (MTDATA), etc., have been used as hole injection and transport materials in the organic EL device. However, the organic EL device comprising the materials has low quantum efficiency and a short operating lifespan, because, when the organic EL device is driven at a high current, thermal stress is generated between an anode and a hole injection layer, thereby rapidly reducing the operating lifespan of the device. Furthermore, movement of holes is great in organic materials used in a hole injection layer, and thus the hole-electron charge balance is broken and quantum efficiency (cd/A) is reduced.
Japanese Patent Application Laid-open No. 2000-077186 discloses fused dibenzofuran-based ring compounds as compounds used in a light-emitting layer of an organic EL device. However, the organic EL device comprising the compounds has high driving voltage and low light-emitting luminance versus driving voltage.
The present inventors have found that by using phosphorescent host compounds having excellent electron transport efficiency in a light-emitting layer of an organic EL device, the hole-electron charge balance is well established in a light-emitting layer, the driving voltage of the device is reduced, and the power efficiency of the device is enhanced. Furthermore, an organic EL device comprising the host material does not need to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.
The objective of the present invention is to provide an organic electroluminescent compound having high current transport efficiency, and an organic electroluminescent device having low driving voltage and enhanced power efficiency by comprising the organic electroluminescent compound in a light-emitting layer.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2014005082-appb-I000001
wherein
X1 and X2 each independently represent CR1R2, NR9, O or S;
Y1 to Y12 each independently represent CR3 or N;
R1 and R2 each independently represent hydrogen, a substituted or unsubstituted (C6-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
R3 represents hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl group, -NR4R5, -SiR6R7R8, a cyano group, a nitro group, or a hydroxyl group;
R4 to R9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono- or polycyclic, (C5-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 heterocycloalkyl group and heteroaryl group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
The organic electroluminescent compound according to the present invention improves the current property of an organic electroluminescent device thereby reducing the driving voltage of the device, and has the advantages of providing an organic EL device having advanced power efficiency. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not need to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present invention relates to an organic electroluminescent compound represented by formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the material.
In the compound of formula 1 of the present invention, preferably, X1 and X2 each independently represent CR1R2 or NR9; Y1 to Y12 each independently represent CR3; R1 to R3 each independently represent hydrogen, a substituted or unsubstituted (C1-C10)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 20-membered heteroaryl group, -SiR6R7R8, a substituted or unsubstituted (C3-C30)cycloalkyl group, or a cyano group; and R4 to R9 each independently represent a substituted or unsubstituted (C1-C6)alkyl group, a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 20-membered heteroaryl group.
In the compound of formula 1 of the present invention, more preferably, R1 and R2 each independently represent an unsubstituted (C1-C10)alkyl group or an unsubstituted (C6-C15)aryl group; R6 to R8 each independently represent an unsubstituted (C1-C6)alkyl group or an unsubstituted (C6-C15)aryl group; and R9 represents a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl(ene) 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, iso-propoxy, 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. “5- to 7-membered heterocycloalkyl” is a cycloalkyl having at least one heteroatom selected from B, N, O, S, P(=O), Si and P, preferably O, S and N, and 5 to 7 ring backbone atoms, 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 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 group having at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P, and 3 to 30 ring backbone atoms; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; has preferably 3 to 20, more preferably 3 to 15 ring backbone atoms; 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, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. “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. Substituents of the substituted alkyl group, the substituted cycloalkyl group, the substituted aryl group, the substituted heteroaryl group, the substituted heterocycloalkyl group, and the substituted mono- or polycyclic (C5-C30) alicyclic or aromatic ring in R1 to R9 of formula 1 each independently are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl group which is unsubstituted or substituted with halogen(s); a (C1-C30)alkoxy group; a (C6-C30)aryl group; a 5- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30)aryl group; a (C3-C30)cycloalkyl group; a 5- to 7-membered heterocycloalkyl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; a (C2-C30)alkenyl group; (C2-C30)alkynyl group; a cyano group; a di(C1-C30)alkylamino group; a di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; a (C1-C30)alkyl(C6-C30)aryl group; a carboxyl group; a nitro group; and a hydroxyl group.
The organic electroluminescent compounds according to the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2014005082-appb-I000002
Figure PCTKR2014005082-appb-I000003
Figure PCTKR2014005082-appb-I000004
Figure PCTKR2014005082-appb-I000005
Figure PCTKR2014005082-appb-I000006
Figure PCTKR2014005082-appb-I000007
Figure PCTKR2014005082-appb-I000008
Figure PCTKR2014005082-appb-I000009
Figure PCTKR2014005082-appb-I000010
Figure PCTKR2014005082-appb-I000011
Figure PCTKR2014005082-appb-I000012
Figure PCTKR2014005082-appb-I000013
Figure PCTKR2014005082-appb-I000014
Figure PCTKR2014005082-appb-I000015
Figure PCTKR2014005082-appb-I000016
Figure PCTKR2014005082-appb-I000017
Figure PCTKR2014005082-appb-I000018
Figure PCTKR2014005082-appb-I000019
Figure PCTKR2014005082-appb-I000020
Figure PCTKR2014005082-appb-I000021
The organic electroluminescent compounds according to the present invention 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:
Scheme 1
Figure PCTKR2014005082-appb-I000022
The present invention further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material. The material can be comprised of the organic electroluminescent compound of the present invention alone, or can further include conventional materials generally included in organic electroluminescent materials.
The organic electroluminescent device according to the present invention may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one organic electroluminescent compound of formula 1.
One of the first electrode and the second electrode can be an anode and the other can be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, and an electron blocking layer.
The light-emitting layers can include the organic electroluminescent compound of the present invention. When used in the light-emitting layer, the organic electroluminescent compounds of the present invention can be included as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present invention may further comprise at least one other compounds as host materials, in addition to the organic electroluminescent compound of the present invention, and may further include at least one dopant.
If the organic electroluminescent compound of the present invention is included as the host material (a first host material) in the light-emitting layer, other compounds may be included as a second host material. The first host material and the second host material may be in the range of 1:99 to 99:1 in a weight ratio.
The second host material, which is other compounds in addition to the organic electroluminescent compound of the present invention, can be any of the known phosphorescent hosts and preferably, is selected from the group consisting of the compounds of the following formulae 2 to 6 in view of luminescent efficiency:
Figure PCTKR2014005082-appb-I000023
Figure PCTKR2014005082-appb-I000024
Figure PCTKR2014005082-appb-I000025
Figure PCTKR2014005082-appb-I000026
Figure PCTKR2014005082-appb-I000027
wherein
Cz represents the following structure:
Figure PCTKR2014005082-appb-I000028
X represents -O- or -S-;
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- or 30-membered heteroaryl group, or R25R26R27Si-; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group;
L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- or 30-membered heteroarylene group;
M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group;
Y1 and Y2 each independently represent -O-, -S-, -N(R31)- or -C(R32)(R33)-; and Y1 and Y2 are not simultaneously present;
R31 to R33 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-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 R32 and R33 may be the same or different;
h and i each independently represent an integer of 1 to 3;
j, k, l and m each independently represent an integer of 0 to 4;
where h, i, j, k, l or m is an integer of 2 or more, each (Cz-L4), each (Cz), each R21, each R22, each R23 or each R24 is the same or different.
Specifically, the second host material includes the following:
Figure PCTKR2014005082-appb-I000029
Figure PCTKR2014005082-appb-I000030
Figure PCTKR2014005082-appb-I000031
Figure PCTKR2014005082-appb-I000032
Figure PCTKR2014005082-appb-I000033
Figure PCTKR2014005082-appb-I000034
Figure PCTKR2014005082-appb-I000035
Figure PCTKR2014005082-appb-I000036
Figure PCTKR2014005082-appb-I000037
Figure PCTKR2014005082-appb-I000038
Figure PCTKR2014005082-appb-I000039
Figure PCTKR2014005082-appb-I000040
Figure PCTKR2014005082-appb-I000041
Figure PCTKR2014005082-appb-I000042
Figure PCTKR2014005082-appb-I000043
Figure PCTKR2014005082-appb-I000044
Figure PCTKR2014005082-appb-I000045
wherein TPS represents triphenylsilyl.
The dopants contained in the organic electroluminescent device of the present invention are preferably one or more phosphorescent dopants. The phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not specifically limited, but preferably may be selected from complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably 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 may be selected from the group consisting of the compounds represented by the following formulae 7 to 9:
Figure PCTKR2014005082-appb-I000046
Figure PCTKR2014005082-appb-I000047
Figure PCTKR2014005082-appb-I000048
wherein
L is selected from the following structures:
Figure PCTKR2014005082-appb-I000049
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; R101 to R109 and R111 to R123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, a cyano group, or a substituted or unsubstituted (C1-C30)alkoxy group; R120 to R123 are linked to an adjacent substituent(s) to form a fused ring, for example, quinoline; R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; when R124 to R127 are aryl groups, they are linked to an adjacent substituent(s) to form a fused ring, for example, fluorene; R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, or a (C6-C30)aryl group; f and g each independently represent an integer of 1 to 3; where f or g is an integer of 2 or more, each R100 may be the same or different; and n represents an integer of 1 to 3.
The phosphorescent dopant material includes the following:
Figure PCTKR2014005082-appb-I000050
Figure PCTKR2014005082-appb-I000051
Figure PCTKR2014005082-appb-I000052
Figure PCTKR2014005082-appb-I000053
Figure PCTKR2014005082-appb-I000054
Figure PCTKR2014005082-appb-I000055
Figure PCTKR2014005082-appb-I000056
Figure PCTKR2014005082-appb-I000057
Figure PCTKR2014005082-appb-I000058
Figure PCTKR2014005082-appb-I000059
Figure PCTKR2014005082-appb-I000060
Figure PCTKR2014005082-appb-I000061
Figure PCTKR2014005082-appb-I000062
Figure PCTKR2014005082-appb-I000063
Figure PCTKR2014005082-appb-I000065
Figure PCTKR2014005082-appb-I000066
Figure PCTKR2014005082-appb-I000067
Figure PCTKR2014005082-appb-I000068
Figure PCTKR2014005082-appb-I000069
Figure PCTKR2014005082-appb-I000070
The present invention further provides the composition for the organic electroluminescent device. The composition comprises the compounds of the present invention as a host material.
Furthermore, the organic electroluminescent device of the present invention comprises a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises a light-emitting layer and the light-emitting layer may comprise the composition for the organic electroluminescent device of the present invention.
The organic electroluminescent device of the present invention comprises the organic electroluminescent compounds of formula 1 and may further include 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 invention, the organic layer may further comprise, in addition to the organic electroluminescent compounds 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 d-transition elements of the Periodic Table, or at least one complex compound comprising the metal. Furthermore, the organic layer may further comprise a light-emitting layer and a charge-generating layer.
In addition, the organic electroluminescent device of the present invention 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, besides the organic electroluminescent compound of the present invention; and may further include a yellow or orange light-emitting layer, if necessary.
Preferably, in the organic electroluminescent device of the present invention, at least one layer (hereinafter, "a surface layer”) selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s). Specifically, it is preferred that a chalcogenide (includes oxides) layer of silicon or aluminum is placed on an anode surface of a light-emitting medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer. The surface layer provides operating 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.
Preferably, in the organic electroluminescent device of the present invention, a mixed region of an electron transport compound and an 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 a light-emitting medium. Further, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to a light-emitting 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 organic electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer constituting the organic electroluminescent device of the present invention, dry film-forming methods, such as vacuum deposition, sputtering, plasma, ion plating methods, etc., or wet film-forming methods, such as spin coating, dip coating, flow coating methods, etc., can be used.
When using a wet film-forming method, a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
Hereinafter, the organic electroluminescent compound of the present invention, the preparation method of the compound, and the luminescent properties of the device comprising the compound will be explained in detail with reference to the following examples:
Example 1: Preparation of compound H-6
Figure PCTKR2014005082-appb-I000071
Preparation of compound C-2
Compound C-1 (40.0 g, 181.81 mmol), 2-bromonitrobenzene (40.4 g, 199.99 mmol) and tetrakis(triphenylphosphine)palladium(O) [Pd(PPh3)4] (10.5 g, 9.09 mmol) were dissolved in 2M K2CO3 (230.0 mL), toluene (900.0 mL) and ethanol (230.0mL) in a flask and the reaction mixture was refluxed at 120°C for 10 hrs. After completing the reaction, the organic layer was extracted with ethyl acetate (EA), the remaining moisture of the organic layer was removed by using MgSO4. The product was dried and separated through column to obtain compound C-2 (43.0 g, 95 %).
Preparation of compound C-3
Compound C-2 (43.0 g, 172.51 mmol) and triphenylphosphine (PPh3) (113.0 g, 431.0 mmol) were dissolved in dichlorobenzene (560.0 mL) and the reaction mixture was reflux at 220°C for 12 hrs. After completing the reaction, dichlorobenzene was removed by distillation and the product was separated through column to obtain compound C-3 (33.0 g, 88 %).
Preparation of compound C-4
Compound C-3 (31.0 g, 142.0 mmol) was dissolved in dimethylformamide (DMF)(600.0 mL) and cooled to 0°C. A solution of N-bromosucciniminde (NBS) (25.4 g, 142.0 mmol) dissolved in DMF (200.0 mL) was slowly added to the mixture. After stirring the mixture at room temperature for 3 hours and completing the reaction, the organic layer was extracted with dichloromethane and distilled water. The remaining moisture of the organic layer was removed by using MgSO4. The product was dried and separated through column to obtain compound C-4 (24.0 g, 57 %).
Preparation of compound C-5
Compound C-4 (19.0 g, 64.15 mmol), iodobenzene (7.5 K3PO4 mL, 67.36 mmol), CuI (6.1 g, 22.07 mmol), ethylenediamine (EDA) (8.66 mL, 12.83 mmol) and K3PO4 (27.0 g, 12.83 mmol) were dissolved in toluene (320.0 mL). The reaction mixture was reflux at 120°C for 12 hrs. After completing the reaction, the organic layer was extracted with dichloromethane. The product was separated through column to obtain compound C-5 (4.9 g, 20 %).
Preparation of compound C-6
Compound C-5 (4.9 g, 13.24 mmol), 2-chloroaniline (2.8 mL, 26.48 mmol), palladium(II) acetate [Pd(OAc)2] (0.12 g, 0.523 mmol), 50% t-butylphosphine [P(t-Bu)3] (0.51 mL, 1.059 mmol) and sodium t-butoxide (tBuONa) (3.2 g, 33.1 mmol) were dissolved in toluene (66.0 mL). The reaction mixture was reflux at 120°C for 3 hrs. After completing the reaction, the organic layer was extracted with dichloromethane and distilled water. The product was separated through column to obtain compound C-6 (4.0 g, 72 %).
Preparation of compound C-7
Compound C-6 (4.0 g, 9.54 mmol), Pd(OAc)2 (0.1 g, 0.477 mmol), ligand (0.35 g, 0.95 mmol) and K2CO3 (7.77 g, 23.87 mmol) were dissolved in N-methylpyrrolidone (NMP) (50.0 mL). The reaction mixture was reflux at 220°C for 3 hrs. After completing the reaction, the organic layer was extracted with dichloromethane and distilled water. The product was separated through column to obtain compound C-7 (3.0 g, 82 %).
Preparation of compound H-6
Compound C-7 (4.0 g, 10.46 mmol) and compound C-10 (3.0 g, 11.5 mmol) were dissolved in DMF (50.0 mL) and NaH (1.25 g, 31.4 mmol; 60% in mineral oil ) was added to the mixture. The reaction mixture was stirred at room temperature for 12 hours, and methanol and distilled water were added to the mixture. The obtained solid was filtered under reduced pressure and separated through column to obtain compound H-6 (3.0 g, 47 %).
Example 2: Preparation of compound H-7
Compound C-7 (3.0 g, 7.84 mmol), compound C-8 (2.26 g, 7.84 mmol), Pd(OAc)2 (0.7 g, 3.14 mmol), 50% t-butylphosphine (3.0 mL, 6.27 mmol) and Cs2CO3 (7.67 g, 23.53 mmol) were dissolved in o-xylene (40.0 mL). The reaction mixture was reflux at 150°C for 4 hrs. After completing the reaction, the solid was extracted with methanol and filtered. The product was separated through column to obtain compound H-7 (1.1 g, 24 %).
Device Example 1: Production of an OLED device by using
the organic electroluminescent compound according to the present invention
An organic light-emitting diode (OLED) device comprising the organic electroluminescent compound according to the present invention was produced as follows: A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an OLED device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1’-([1,1’-biphenyl]-4,4’-diyl)bis(N1-(naphthalene-1-yl)-N4,N4-diphenylbenzene-1,4-diamine) was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Then, N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was 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 hole transport layer having a thickness of 20 nm on the hole injection layer. Compound H-6 was introduced as a host into one cell of the vacuum vapor depositing apparatus, and compound D-87 as a dopant was introduced into another cell. The two materials were evaporated at different rates and the dopant was deposited in a doping amount of 4 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidiazole was introduced into one cell, and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rates and were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
The produced OLED device showed red emission having a luminance of 1000 cd/m2 at 3.4 V. Furthermore, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 80 hours.
Device Example 2: Production of an OLED device by using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound H-7 was used as a host and compound D-88 was used as a dopant in a light-emitting material.
The produced OLED device showed red emission having a luminance of 1000 cd/m2 at 3.6 V. Furthermore, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 40 hours.
Comparative Example 1: Production of an OLED device by using
conventional light-emitting materials
An OLED device was produced in the same manner as in Device Example 1, except that compound E-1 was used as a host and compound D-11 was used as a dopant in a light-emitting material.
The produced OLED device showed red emission having a luminance of 1000 cd/m2 at 4.0 V. Furthermore, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 20 hours.
Figure PCTKR2014005082-appb-I000072
The organic electroluminescent compound according to the present invention reduces the driving voltage of an organic electroluminescent device by improving the current property of the device. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not need to comprise a hole blocking layer and improves lifespan.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014005082-appb-I000073
    Wherein
    X1 and X2 each independently represent CR1R2, NR9, O or S;
    Y1 to Y12 each independently represent CR3 or N;
    R1 and R2 each independently represent hydrogen, a substituted or unsubstituted (C6-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
    R3 represents hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl group, -NR4R5, -SiR6R7R8, a cyano group, a nitro group, or a hydroxyl group;
    R4 to R9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono- or polycyclic, (C5-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 heterocycloalkyl group and heteroaryl group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted alkyl group, the substituted cycloalkyl group, the substituted aryl group, the substituted heteroaryl group, the substituted heterocycloalkyl group, and the substituted mono- or polycyclic, (C5-C30) alicyclic or aromatic ring in R1 to R9 of formula 1 are each independently at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl group which is unsubstituted or substituted with a halogen; a (C1-C30)alkoxy group; a (C6-C30)aryl group; a 5- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30)aryl group; a (C3-C30)cycloalkyl group; a 5- to 7-membered heterocycloalkyl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a cyano group; a di(C1-C30)alkylamino group; a di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; a (C1-C30)alkyl(C6-C30)aryl group; a carboxyl group; a nitro group; and a hydroxyl group.
  3. The organic electroluminescent compound according to claim 1, wherein X1 and X2 each independently represent CR1R2 or NR9; Y1 to Y12 each independently represent CR3; R1 to R3 each independently represent hydrogen, a substituted or unsubstituted (C1-C10)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 20-membered heteroaryl group, -SiR6R7R8, a substituted or unsubstituted (C3-C30)cycloalkyl group, or a cyano group; and R4 to R9 each independently represent a substituted or unsubstituted (C1-C6)alkyl group, a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 20-membered heteroaryl group.
  4. The organic electroluminescent compound according to claim 1, wherein R1 and R2 each independently represent an unsubstituted (C1-C10)alkyl group or an unsubstituted (C6-C15)aryl group; R6 to R8 each independently represent an unsubstituted (C1-C6)alkyl group or an unsubstituted (C6-C15)aryl group; and R9 represents a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group.
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of the following compounds:
    Figure PCTKR2014005082-appb-I000074
    Figure PCTKR2014005082-appb-I000075
    Figure PCTKR2014005082-appb-I000076
    Figure PCTKR2014005082-appb-I000077
    Figure PCTKR2014005082-appb-I000078
    Figure PCTKR2014005082-appb-I000079
    Figure PCTKR2014005082-appb-I000080
    Figure PCTKR2014005082-appb-I000081
    Figure PCTKR2014005082-appb-I000082
    Figure PCTKR2014005082-appb-I000083
    Figure PCTKR2014005082-appb-I000084
    Figure PCTKR2014005082-appb-I000085
    Figure PCTKR2014005082-appb-I000086
    Figure PCTKR2014005082-appb-I000087
    Figure PCTKR2014005082-appb-I000088
    Figure PCTKR2014005082-appb-I000089
    Figure PCTKR2014005082-appb-I000090
    Figure PCTKR2014005082-appb-I000091
    Figure PCTKR2014005082-appb-I000092
    Figure PCTKR2014005082-appb-I000093
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
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