WO2015099486A1 - 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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WO2015099486A1
WO2015099486A1 PCT/KR2014/012895 KR2014012895W WO2015099486A1 WO 2015099486 A1 WO2015099486 A1 WO 2015099486A1 KR 2014012895 W KR2014012895 W KR 2014012895W WO 2015099486 A1 WO2015099486 A1 WO 2015099486A1
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group
substituted
unsubstituted
organic electroluminescent
aryl
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PCT/KR2014/012895
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French (fr)
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Hee-Ryong Kang
Mi-Ja Lee
Hyun-Ju Kang
Nam-Kyun Kim
Chi-Sik Kim
Bitnari Kim
Young-Jun Cho
Kyung-Joo Lee
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority to JP2016538573A priority Critical patent/JP6525381B2/en
Priority to CN201480069405.9A priority patent/CN105849107B/en
Publication of WO2015099486A1 publication Critical patent/WO2015099486A1/en

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    • H05B33/00—Electroluminescent light sources
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    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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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 organic EL device generally comprises an anode, a cathode, and an organic layer formed between the two electrodes and emits light by the recombination of holes injected from an anode and electrons injected from a cathode.
  • the organic layer of the organic EL device may be composed of a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), etc.; the materials used in the organic layer can be classified into a hole injection material, a hole transport material, a light-emitting material, an electron transport material, an electron injection material, etc.
  • the light-emitting material is required to have the following features: high quantum efficiency, high movement degree of an electron and a hole, formability of a uniform light-emitting material layer, and stability.
  • the light-emitting material is classified into blue light-emitting materials, green light-emitting materials, or red light-emitting materials according to the light-emitting color, and further includes yellow light-emitting materials or orange light-emitting materials.
  • the light-emitting materials are classified into fluorescent materials (singlet excited state) and phosphorescent materials (triplet excited state) according to the excited state.
  • the fluorescent materials were initially used in an organic EL device. However, phosphorescent materials have efficiency for changing electricity into light (luminescent efficiency) by four (4) times over fluorescent materials, reduce consumption power, and increase lifespan. Thus, development of phosphorescent materials is widely being conducted.
  • 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 since the host material greatly influences the efficiency and performance of a light-emitting device. In conventional technique, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known 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 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 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.
  • the materials constituting the organic layers in the device should be suitably selected.
  • Korean Patent No. 10-1082144 discloses the organic electroluminescent compound comprising a specific fused heterocyclic structure as a host.
  • the organic EL devices comprising the compound recited in the above publication still do not satisfy power efficiency, luminescent efficiency, lifespan, etc.
  • the present inventors have tried to find organic electroluminescent compounds that can provide the organic EL device with properties superior to the compounds recited in the above publication and have found the compound providing the device with high luminescent efficiency and excellent device properties.
  • the object of the present invention is to provide organic electroluminescent compounds having high luminescent efficiency and to provide an organic EL device comprising the organic electroluminescent compounds and having long driving lifespan, and improved power efficiency and current efficiency.
  • Korean Patent No. 10-1082144 discloses the compound wherein a HOMO site is directly connected to a LUMO site without a linker.
  • the compound is in the form of an indolocarbazole structure, not a benzoindolocarbazole, and shows a remarkable characteristic difference as a red host.
  • the structures of triazine, pyridine, pyrimidine, quinoline, etc., bonded to indolocarbazole are used as a phosphorescent green host, and the structures of quinazoline, quinoxaline, etc., bonded to benzoindolocarbazole have excellent features as only a phosphorescent red host.
  • the red light-emitting device comprising the material of the present invention provides improved properties compared with the device comprising an indolocarbazole derivative having no phenyl as a linker which is supplied by other companies.
  • the compound of the present invention comprising benzoindolocarbazole bonded to quinoxaline, quinazoline, etc., by a linker, is structurally different from the compounds supplied by other companies in the chemical structure and has maximized efficiency properties.
  • L 1 represents a substituted or unsubstituted (C6-C30)arylene group
  • Ring A or B represents benzene or naphthalene, with the proviso that A and B do not simultaneously represent benzene;
  • X represents NR 6 , -CR 7 R 8 , O, or S;
  • Y 1 and Y 2 each independently represent -CR 9 - or -N-, and if Y 1 represents -N-, Y 2 represents -CR 9 -, and if Y 1 represents -CR 9 -, Y 2 represents -N-;
  • R 1 to R 5 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted (C6-C30)arylamine group, -NR 10 R 11 , or -SiR 12 R 13 R 14 ;
  • R 1 , R 2 and R 5 are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
  • R 6 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 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 10 R 11 , -SiR 12 R 13 R 14 , a cyano group, a nitro group, or a hydroxyl group;
  • R 10 and R 11 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
  • R 12 to R 14 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 3- 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 (C3-C30) alicyclic or aromatic ring;
  • the carbon atom(s) of the alicyclic or aromatic ring may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • a represents an integer of 1 to 4; where a is an integer of 2 or more, each R 1 is the same or different;
  • a or B represents benzene
  • b or c represents an integer of 1 to 4.
  • a or B represents naphthalene
  • b or c represents an integer of 1 to 6; where b or c is an integer of 2 or more, each R 2 or each R 5 is the same or different.
  • the organic electroluminescent compounds according to the present invention have high luminescent efficiency and an excellent lifespan property, and thus the organic EL device comprising the compounds has long driving lifespan, and good current efficiency and power efficiency.
  • the present invention relates to an organic electroluminescent compound represented by formula 1, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic EL device comprising the material.
  • (C1-C30)alkyl(ene) 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.
  • (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.
  • L 1 , X, Y 1 , Y 2 , R 1 to R 5 , a, b, and c are as defined in formula 1.
  • L 1 , X, Y 1 , Y 2 , R 1 to R 5 , a, b, and c are as defined in formula 1.
  • L 1 , X, Y 1 , Y 2 , R 1 to R 5 , a, b, and c are as defined in formula 1.
  • L 1 represents a (C6-C20)arylene group which is unsubstituted or substituted by a (C1-C6)alkyl group
  • R 1 to R 5 each independently represent hydrogen, or a substituted or unsubstituted (C6-C20)aryl group
  • R 6 to R 9 each independently represent a substituted or unsubstituted (C1-C6)alkyl group, or a substituted or unsubstituted (C6-C20)aryl group.
  • the compound of formula 1 can be selected from the group consisting of the following compounds:
  • 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 a hole blocking layer.
  • the organic electroluminescent compound of formula 1 of the present invention can be included as a host material in the light-emitting layer.
  • the light-emitting layer may further include at least one dopant and, if necessary, may comprise other compounds, in addition to the organic electroluminescent compound of formula 1 of the present invention, as a second host material.
  • the present invention further provides materials for preparing an organic EL device.
  • the materials comprise the first and second host materials.
  • the first host material includes the organic electroluminescent compound of the present invention.
  • 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 can be any of the known phosphorescent hosts and preferably is selected from the group consisting of the compounds of the following formulae 5 to 9:
  • 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 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 dopant included in the organic electroluminescent device of the present invention may be selected from the group consisting of the compounds represented by the following formulae 10 to 12:
  • 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 which is 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 substitute
  • the phosphorescent dopant material includes the following:
  • the organic layer of 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 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 (including 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 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 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 using the organic electroluminescent compound of 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 was then stored in isopropanol. Next, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • ITO indium tin oxide
  • N 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 the pressure in the chamber of the apparatus was then controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a 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-61 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.
  • 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidiazole was then 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.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the produced OLED device showed red emission having a current density of 8.1 mA/cm 2 and a luminance of 990 cd/m 2 at 3.5 V. Furthermore, the time taken to be reduced to 90 % of the luminescence at a luminance of 5,000nit was at least 130 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except that compound H-60 was used as a host in a light-emitting material.
  • the produced OLED device showed red emission having a current density of 8.2 mA/cm 2 and a luminance of 1050 cd/m 2 at 3.4 V. Furthermore, the time taken to be reduced to 90 % of the luminescence at a luminance of 5,000nit was at least 130 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except that compound H-10 as a host and compound D-88 as a dopant were used in a light-emitting material.
  • the produced OLED device showed red emission having a current density of 12.2 mA/cm 2 and a luminance of 920 cd/m 2 at 3.6 V. Furthermore, the time taken to be reduced to 90 % of the luminescence at a luminance of 5,000nit was at least 110 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except that compound R-1 was used as a host in a light-emitting material.
  • the produced OLED device showed red emission having a current density of 8.0 mA/cm 2 and a luminance of 1000 cd/m 2 at 4.7 V. Furthermore, the time taken to be reduced to 90 % of the luminescence at a luminance of 5,000nit was at least 10 hours.
  • the organic electroluminescent compound of the present invention has excellent luminescent efficiency and the organic electroluminescent device comprising the organic electroluminescent compound of the present invention provides long driving lifespan, and improved current efficiency and power efficiency.

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 can be used in a light-emitting layer and has excellent luminescent efficiency; and an organic electroluminescent device comprising the organic electroluminescent compounds of the present invention has long lifespan, and improved current efficiency and power efficiency.

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 organic EL device generally comprises an anode, a cathode, and an organic layer formed between the two electrodes and emits light by the recombination of holes injected from an anode and electrons injected from a cathode. The organic layer of the organic EL device may be composed of a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), etc.; the materials used in the organic layer can be classified into a hole injection material, a hole transport material, a light-emitting material, an electron transport material, an electron injection material, etc.
The most important factor determining luminescent efficiency in the organic EL device is the light-emitting material. The light-emitting material is required to have the following features: high quantum efficiency, high movement degree of an electron and a hole, formability of a uniform light-emitting material layer, and stability. The light-emitting material is classified into blue light-emitting materials, green light-emitting materials, or red light-emitting materials according to the light-emitting color, and further includes yellow light-emitting materials or orange light-emitting materials. The light-emitting materials are classified into fluorescent materials (singlet excited state) and phosphorescent materials (triplet excited state) according to the excited state. The fluorescent materials were initially used in an organic EL device. However, phosphorescent materials have efficiency for changing electricity into light (luminescent efficiency) by four (4) times over fluorescent materials, reduce consumption power, and increase lifespan. Thus, development of phosphorescent materials is widely being conducted.
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 since the host material greatly influences the efficiency and performance of a light-emitting device. In conventional technique, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known 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 host materials has no advantage in terms of power efficiency (lm/W). (3) Furthermore, the operating lifespan and luminescent 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 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 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.
Thus, in order to embody excellent properties of the organic EL device, the materials constituting the organic layers in the device, in particular the host or dopant, should be suitably selected. Meanwhile, Korean Patent No. 10-1082144 discloses the organic electroluminescent compound comprising a specific fused heterocyclic structure as a host. However, the organic EL devices comprising the compound recited in the above publication still do not satisfy power efficiency, luminescent efficiency, lifespan, etc. Thus, the present inventors have tried to find organic electroluminescent compounds that can provide the organic EL device with properties superior to the compounds recited in the above publication and have found the compound providing the device with high luminescent efficiency and excellent device properties.
The object of the present invention is to provide organic electroluminescent compounds having high luminescent efficiency and to provide an organic EL device comprising the organic electroluminescent compounds and having long driving lifespan, and improved power efficiency and current efficiency.
Korean Patent No. 10-1082144 discloses the compound wherein a HOMO site is directly connected to a LUMO site without a linker. The compound is in the form of an indolocarbazole structure, not a benzoindolocarbazole, and shows a remarkable characteristic difference as a red host. Generally, the structures of triazine, pyridine, pyrimidine, quinoline, etc., bonded to indolocarbazole are used as a phosphorescent green host, and the structures of quinazoline, quinoxaline, etc., bonded to benzoindolocarbazole have excellent features as only a phosphorescent red host. Thus, the red light-emitting device comprising the material of the present invention provides improved properties compared with the device comprising an indolocarbazole derivative having no phenyl as a linker which is supplied by other companies. Furthermore, the compound of the present invention, comprising benzoindolocarbazole bonded to quinoxaline, quinazoline, etc., by a linker, is structurally different from the compounds supplied by other companies in the chemical structure and has maximized efficiency properties.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2014012895-appb-I000001
wherein
L1 represents a substituted or unsubstituted (C6-C30)arylene group;
Ring A or B represents benzene or naphthalene, with the proviso that A and B do not simultaneously represent benzene;
X represents NR6, -CR7R8, O, or S;
Y1 and Y2 each independently represent -CR9- or -N-, and if Y1 represents -N-, Y2 represents -CR9-, and if Y1 represents -CR9-, Y2 represents -N-;
R1 to R5 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted (C6-C30)arylamine group, -NR10R11, or -SiR12R13R14;
R1, R2 and R5 are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
R6 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 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, -NR10R11, -SiR12R13R14, a cyano group, a nitro group, or a hydroxyl group;
R10 and R11 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
R12 to R14 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 3- 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 (C3-C30) alicyclic or aromatic ring;
the carbon atom(s) of the alicyclic or aromatic ring may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
the heteroaryl(ene) and heterocycloalkyl groups contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P;
a represents an integer of 1 to 4; where a is an integer of 2 or more, each R1 is the same or different;
if A or B represents benzene, b or c represents an integer of 1 to 4; and
if A or B represents naphthalene, b or c represents an integer of 1 to 6; where b or c is an integer of 2 or more, each R2 or each R5 is the same or different.
The organic electroluminescent compounds according to the present invention have high luminescent efficiency and an excellent lifespan property, and thus the organic EL device comprising the compounds has long driving lifespan, and good current efficiency and power efficiency.
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, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic EL device comprising the material.
Herein, “(C1-C30)alkyl(ene)” 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. “(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. “3- 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 3 to 7, preferably 5 to 7 ring backbone atoms, and includes tetrahydrofuran, 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 (C1-C30)alkyl group, the substituted (C3-C30)cycloalkyl group, the substituted (C3-C30)cycloalkenyl group, the substituted 3- to 7-membered heterocycloalkyl group, the substituted (C6-C30)aryl(ene) group, the substituted 5- to 30-membered heteroaryl(ene) group, the substituted (C6-C30)aryl(C1-C30)alkyl group, and the substituted mono- or polycyclic (C3-C30) alicyclic or aromatic ring in L1, X, Y1, Y2, and R1 to R5 of the formulae are each independently at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a (C1-C30)alkoxy group; a (C1-C30)alkylthio group; a (C3-C30)cycloalkyl group; a (C3-C30)cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryloxy group; a (C6-C30)arylthio group; a 3- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30)aryl group; a (C6-C30)aryl group which is unsubstituted or substituted with a 3- to 30-membered heteroaryl 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; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a (C1-C30)alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30)arylcarbonyl 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; and a (C1-C30)alkyl(C6-C30)aryl group.
The compound of formula 1 is represented by the following formula 2:
Figure PCTKR2014012895-appb-I000002
wherein
L1, X, Y1, Y2, R1 to R5, a, b, and c are as defined in formula 1.
The compound of formula 1 is represented by the following formula 3:
Figure PCTKR2014012895-appb-I000003
wherein
L1, X, Y1, Y2, R1 to R5, a, b, and c are as defined in formula 1.
The compound of formula 1 is represented by the following formula 4:
Figure PCTKR2014012895-appb-I000004
wherein
L1, X, Y1, Y2, R1 to R5, a, b, and c are as defined in formula 1.
In the compound of formula 1, 2, 3, and 4, preferably, L1 represents a (C6-C20)arylene group which is unsubstituted or substituted by a (C1-C6)alkyl group; R1 to R5 each independently represent hydrogen, or a substituted or unsubstituted (C6-C20)aryl group; R6 to R9 each independently represent a substituted or unsubstituted (C1-C6)alkyl group, or a substituted or unsubstituted (C6-C20)aryl group.
The compound of formula 1 can be selected from the group consisting of the following compounds:
Figure PCTKR2014012895-appb-I000005
Figure PCTKR2014012895-appb-I000006
Figure PCTKR2014012895-appb-I000007
Figure PCTKR2014012895-appb-I000008
Figure PCTKR2014012895-appb-I000009
Figure PCTKR2014012895-appb-I000010
Figure PCTKR2014012895-appb-I000011
Figure PCTKR2014012895-appb-I000012
Figure PCTKR2014012895-appb-I000013
Figure PCTKR2014012895-appb-I000014
Figure PCTKR2014012895-appb-I000015
Figure PCTKR2014012895-appb-I000016
Figure PCTKR2014012895-appb-I000017
Figure PCTKR2014012895-appb-I000018
Figure PCTKR2014012895-appb-I000019
Figure PCTKR2014012895-appb-I000020
Figure PCTKR2014012895-appb-I000021
Figure PCTKR2014012895-appb-I000022
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:
Reaction scheme 1
Figure PCTKR2014012895-appb-I000023
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 a hole blocking layer.
The organic electroluminescent compound of formula 1 of the present invention can be included as a host material in the light-emitting layer. Preferably, the light-emitting layer may further include at least one dopant and, if necessary, may comprise other compounds, in addition to the organic electroluminescent compound of formula 1 of the present invention, as a second host material.
The present invention further provides materials for preparing an organic EL device. The materials comprise the first and second host materials. The first host material includes the organic electroluminescent compound of the present invention. 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 can be any of the known phosphorescent hosts and preferably is selected from the group consisting of the compounds of the following formulae 5 to 9:
Figure PCTKR2014012895-appb-I000024
Figure PCTKR2014012895-appb-I000025
Figure PCTKR2014012895-appb-I000026
Figure PCTKR2014012895-appb-I000027
Figure PCTKR2014012895-appb-I000028
wherein
Cz represents the following structure:
Figure PCTKR2014012895-appb-I000029
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 PCTKR2014012895-appb-I000030
Figure PCTKR2014012895-appb-I000031
Figure PCTKR2014012895-appb-I000032
Figure PCTKR2014012895-appb-I000033
Figure PCTKR2014012895-appb-I000034
Figure PCTKR2014012895-appb-I000035
Figure PCTKR2014012895-appb-I000036
Figure PCTKR2014012895-appb-I000037
Figure PCTKR2014012895-appb-I000038
Figure PCTKR2014012895-appb-I000039
Figure PCTKR2014012895-appb-I000040
Figure PCTKR2014012895-appb-I000041
Figure PCTKR2014012895-appb-I000042
Figure PCTKR2014012895-appb-I000043
Figure PCTKR2014012895-appb-I000044
Figure PCTKR2014012895-appb-I000045
Figure PCTKR2014012895-appb-I000046
wherein TPS represents triphenylsilyl.
The dopants 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 dopant included in the organic electroluminescent device of the present invention may be selected from the group consisting of the compounds represented by the following formulae 10 to 12:
Figure PCTKR2014012895-appb-I000047
Figure PCTKR2014012895-appb-I000048
Figure PCTKR2014012895-appb-I000049
wherein
L is selected from the following structures:
Figure PCTKR2014012895-appb-I000050
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 which is 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 which is 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 PCTKR2014012895-appb-I000051
Figure PCTKR2014012895-appb-I000052
Figure PCTKR2014012895-appb-I000053
Figure PCTKR2014012895-appb-I000054
Figure PCTKR2014012895-appb-I000055
Figure PCTKR2014012895-appb-I000056
Figure PCTKR2014012895-appb-I000057
Figure PCTKR2014012895-appb-I000058
Figure PCTKR2014012895-appb-I000059
Figure PCTKR2014012895-appb-I000060
Figure PCTKR2014012895-appb-I000061
Figure PCTKR2014012895-appb-I000062
Figure PCTKR2014012895-appb-I000063
Figure PCTKR2014012895-appb-I000064
Figure PCTKR2014012895-appb-I000065
Figure PCTKR2014012895-appb-I000066
Figure PCTKR2014012895-appb-I000067
Figure PCTKR2014012895-appb-I000068
Figure PCTKR2014012895-appb-I000069
Figure PCTKR2014012895-appb-I000070
Figure PCTKR2014012895-appb-I000071
The organic layer of 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.
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 (including 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 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 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 compounds H-61, H-60, H-10, and H-11
Figure PCTKR2014012895-appb-I000072
1) Preparation of compound 1-1
Compound A (100.0 g, 356.0 mmol), 1-naphthyl boronic acid (51.0 g, 297.0 mmol), tetrakis(triphenylphosphine)palladium(O) (Pd(PPh3)4) (11.0 g, 9.0 mmol), 2M K2CO3 (500.0 mL), toluene (1000.0 mL), and ethanol (500.0 mL) in a flask were stirred under reflux for 5 hrs. After completing the reaction, the organic layer was extracted with ethyl acetate (EA) and dried by removing the remaining moisture with MgSO4. The residue was separated via column chromatography to obtain compound 1-1 (70.0 g, 72 %).
2) Preparation of compound 1-2
Compound 1-1 (70.0 g, 213.0 mmol), triphenylphosphine (140.0 g, 533.0 mmol), and dichlorobenzene (1.0 L) were dissolved in a flask and the mixture was refluxed at 150 °C for 6 hrs. After completing the reaction, the mixture was distilled and triturated with methanol (MeOH) to obtain compound 1-2 (40.0 g, 64 %).
3) Preparation of compound 1-3
Compound 1-2 (20.0 g, 67.53 mmol), iodobenzene (15.0 mL, 135.06 mmol), CuI (12.0 g, 33.77 mmol), Cs2CO3 (66.0 g, 202.59 mmol), ethylenediamine (EDA) (2.0 mL, 33.77 mmol), and toluene (400.0 mL) were dissolved in a flask and the mixture was refluxed at 120 °C for 5 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The residue was separated via column chromatography to obtain compound 1-3 (15.0 g, 60 %).
4) Preparation of compound 1-4
Compound 1-3 (26.0 g, 69.84 mmol), 2-chloroaniline (11.0 g, 104.77 mmol), palladium(II) acetate (Pd(OAc)2) (0.6 g, 2.79 mmol), sodium tert-butoxide (NaOtBu) (16.0 g, 174.6 mmol), tri-tert-butylphosphine (P(t-Bu)3) (3.0 mL, 5.58 mmol), and toluene (350.0 mL) were dissolved in a flask and the mixture was refluxed at 120 °C for 5 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The residue was separated via column chromatography to obtain compound 1-4 (19.2 g, 66 %).
5) Preparation of compound 1-5
Compound 1-4 (26.0 g, 69.84 mmol), Pd(OAc)2 (0.6 g, 2.79 mmol), Cs2CO3 (45.0 g, 137.49 mmol), tricyclohexylphosphine tetrafluoroborate (PCy3HBF4) (1.7 g, 4.58 mmol), and toluene (300.0 mL) were dissolved in a flask and the mixture was refluxed at 120 °C for 5 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The residue was separated via column chromatography to obtain compound 1-5 (15.0 g, 88 %).
6) Preparation of compound 1-6
Compound 1-5 (14.0 g, 36.60 mmol), 1-bromo-3-iodobenzene (15.0 g, 54.91 mmol), CuI (3.5 g, 18.30 mmol), K3PO4 (23.0 g, 109.8 mmol), EDA (3.0 mL, 36.60 mmol), and toluene (183.0 mL) were dissolved in a flask and the mixture was refluxed at 120 °C for 5 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The residue was separated via column chromatography to obtain compound 1-6 (12.4 g, 65 %).
7) Preparation of compound 1-7
Compound 1-6 (12.4 g, 23.07 mmol) was dissolved in tetrahydrofuran (THF) (100.0 mL), and n-butyl lithium (n-BuLi) (14.0 mL, 34.61 mmol, 2.5 M in hexane) was slowly added thereto at -78 °C. After 1 hr, triisopropyl borate (8.0 mL, 34.61 mmol) was added to the mixture. After stirring the mixture at room temperature for 12 hrs, distilled water was added thereto. The organic layer was extracted with EA, dried over MgSO4, and distilled under reduced pressure. Compound 1-7 (6.0 g, 52 %) was obtained by recrystallization with EA and hexane.
8) Preparation of compound H-61
Compound 1-7 (7.4 g, 14.73 mmol), compound B (3.0 g, 12.27 mmol), Pd(PPh3)4 (1.4 g, 1.23 mmol), 2M K2CO3 (30.0 mL), toluene (60.0 mL), and ethanol (30.0 mL) in a flask were stirred under reflux for 5 hrs. The mixture was cooled to room temperature and distilled water was added thereto. The organic layer was extracted with EA and dried over MgSO4. The residue was distilled under reduced pressure and recrystallized with EA and MeOH to obtain compound H-61 (2.6 g, 32 %).
9) Preparation of compound H-60
Compound 1-7 (10.0 g, 17.11 mmol), compound B (5.3 g, 22.24 mmol), Pd(PPh3)4 (1.0 g, 0.86 mmol), 2M K2CO3 (50.0 mL), toluene (100.0 mL), and ethanol (50.0 mL) in a flask were stirred under reflux for 5 hrs. The mixture was cooled to room temperature and distilled water was added thereto. The organic layer was extracted with EA and dried over MgSO4. The residue was distilled under reduced pressure and recrystallized with EA and MeOH to obtain compound H-60 (4.1 g, 37 %).
10) Preparation of compound H-10
Compound 1-7 (10.0 g, 17.11 mmol), compound C (3.5 g, 14.25 mmol), Pd(PPh3)4 (0.8 g, 0.712 mmol), 2M K2CO3 (35.0 mL), toluene (70.0 mL), and ethanol (35.0 mL) in a flask were stirred under reflux for 5 hrs. The mixture was cooled to room temperature and distilled water was added thereto. The organic layer was extracted with EA and dried over MgSO4. The residue was distilled under reduced pressure and recrystallized with EA and MeOH to obtain compound H-10 (7.5 g, 79 %).
11) Preparation of compound H-11
Compound 1-7 (13.0 g, 22.2 mmol), compound C (4.5 g, 18.6 mmol), Pd(PPh3)4 (1.0 g, 0.9 mmol), 2M K2CO3 (28.0 mL), toluene (60.0 mL), and ethanol (28.0 mL) in a flask were stirred under reflux for 5 hrs. The mixture was cooled to room temperature and distilled water was added thereto. The organic layer was extracted with EA and dried over MgSO4. The residue was distilled under reduced pressure and recrystallized with EA and MeOH to obtain compound H-11 (2.5 g, 21 %).
The property data of the compounds prepared in Example 1 are provided in Table 1 below:
Table 1
Figure PCTKR2014012895-appb-I000073
Device Example 1: Pro duction of an OLED device by using the
organic electroluminescent com pound according to the present invention
An organic light-emitting diode (OLED) device using the organic electroluminescent compound of 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 was then stored in isopropanol. Next, 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 the pressure in the chamber of the apparatus was then controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Next, 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-61 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. 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidiazole was then 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. Next, 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 current density of 8.1 mA/cm2 and a luminance of 990 cd/m2 at 3.5 V. Furthermore, the time taken to be reduced to 90 % of the luminescence at a luminance of 5,000nit was at least 130 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-60 was used as a host in a light-emitting material.
The produced OLED device showed red emission having a current density of 8.2 mA/cm2 and a luminance of 1050 cd/m2 at 3.4 V. Furthermore, the time taken to be reduced to 90 % of the luminescence at a luminance of 5,000nit was at least 130 hours.
Device Example 3: 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-10 as a host and compound D-88 as a dopant were used in a light-emitting material.
The produced OLED device showed red emission having a current density of 12.2 mA/cm2 and a luminance of 920 cd/m2 at 3.6 V. Furthermore, the time taken to be reduced to 90 % of the luminescence at a luminance of 5,000nit was at least 110 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 R-1 was used as a host in a light-emitting material.
The produced OLED device showed red emission having a current density of 8.0 mA/cm2 and a luminance of 1000 cd/m2 at 4.7 V. Furthermore, the time taken to be reduced to 90 % of the luminescence at a luminance of 5,000nit was at least 10 hours.
Figure PCTKR2014012895-appb-I000074
The organic electroluminescent compound of the present invention has excellent luminescent efficiency and the organic electroluminescent device comprising the organic electroluminescent compound of the present invention provides long driving lifespan, and improved current efficiency and power efficiency.

Claims (8)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014012895-appb-I000075
    wherein
    L1 represents a substituted or unsubstituted (C6-C30)arylene group;
    Ring A or B represents benzene or naphthalene, with the proviso that A and B do not simultaneously represent benzene;
    X represents NR6, -CR7R8, O, or S;
    Y1 and Y2 each independently represent -CR9- or -N-, and if Y1 represents -N-, Y2 represents -CR9-, and if Y1 represents -CR9-, Y2 represents -N-;
    R1 to R5 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted (C6-C30)arylamine group, -NR10R11, or -SiR12R13R14;
    R1, R2 and R5 are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
    R6 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 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, -NR10R11, -SiR12R13R14, a cyano group, a nitro group, or a hydroxyl group;
    R10 and R11 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
    R12 to R14 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 3- 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 (C3-C30) alicyclic or aromatic ring;
    the carbon atom(s) of the alicyclic or aromatic ring may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    the heteroaryl(ene) and heterocycloalkyl groups contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P;
    a represents an integer of 1 to 4; where a is an integer of 2 or more, each R1 is the same or different;
    if A or B represents benzene, b or c represents an integer of 1 to 4; and
    if A or B represents naphthalene, b or c represents an integer of 1 to 6; where b or c is an integer of 2 or more, each R2 or each R5 is the same or different.
  2. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 2:
    Figure PCTKR2014012895-appb-I000076
    wherein
    L1, X, Y1, Y2, R1 to R5, a, b, and c are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 3:
    Figure PCTKR2014012895-appb-I000077
    wherein
    L1, X, Y1, Y2, R1 to R5, a, b, and c are as defined in claim 1.
  4. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 4:
    Figure PCTKR2014012895-appb-I000078
    wherein
    L1, X, Y1, Y2, R1 to R5, a, b, and c are as defined in claim 1.
  5. The organic electroluminescent compound according to any one of claims 1 to 4, wherein L1 represents a (C6-C20)arylene group which is unsubstituted or substituted by a (C1-C6)alkyl group; R1 to R5 each independently represent hydrogen, or a substituted or unsubstituted (C6-C20)aryl group; R6 to R9 each independently represent a substituted or unsubstituted (C1-C6)alkyl group, or a substituted or unsubstituted (C6-C20)aryl group.
  6. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl group, the substituted (C3-C30)cycloalkyl group, the substituted (C3-C30)cycloalkenyl group, the substituted 3- to 7-membered heterocycloalkyl group, the substituted (C6-C30)aryl(ene) group, the substituted 3- to 30-membered heteroaryl(ene) group, the substituted (C6-C30)aryl(C1-C30)alky group, and the substituted mono- or polycyclic (C3-C30) alicyclic or aromatic ring in L1, X, Y1, Y2, and R1 to R5 are each independently at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a (C1-C30)alkoxy group; a (C1-C30)alkylthio group; a (C3-C30)cycloalkyl group; a (C3-C30)cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryloxy group; a (C6-C30)arylthio group; a 3- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30)aryl group; a (C6-C30)aryl group which is unsubstituted or substituted with a 3- to 30-membered heteroaryl 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; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a (C1-C30)alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30)arylcarbonyl 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; and a (C1-C30)alkyl(C6-C30)aryl group.
  7. 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 PCTKR2014012895-appb-I000079
    Figure PCTKR2014012895-appb-I000080
    Figure PCTKR2014012895-appb-I000081
    Figure PCTKR2014012895-appb-I000082
    Figure PCTKR2014012895-appb-I000083
    Figure PCTKR2014012895-appb-I000084
    Figure PCTKR2014012895-appb-I000085
    Figure PCTKR2014012895-appb-I000086
    Figure PCTKR2014012895-appb-I000087
    Figure PCTKR2014012895-appb-I000088
    Figure PCTKR2014012895-appb-I000089
    Figure PCTKR2014012895-appb-I000090
    Figure PCTKR2014012895-appb-I000091
    Figure PCTKR2014012895-appb-I000092
    Figure PCTKR2014012895-appb-I000093
    Figure PCTKR2014012895-appb-I000094
    Figure PCTKR2014012895-appb-I000095
    Figure PCTKR2014012895-appb-I000096
  8. An organic electroluminescent device comprising the compound according to claim 1.
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