WO2014185751A1 - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

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

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WO2014185751A1
WO2014185751A1 PCT/KR2014/004424 KR2014004424W WO2014185751A1 WO 2014185751 A1 WO2014185751 A1 WO 2014185751A1 KR 2014004424 W KR2014004424 W KR 2014004424W WO 2014185751 A1 WO2014185751 A1 WO 2014185751A1
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substituted
unsubstituted
alkyl
membered
aryl
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PCT/KR2014/004424
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French (fr)
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Hee-Ryong Kang
Mi-Ja Lee
Su-Hyun Lee
Young-Kwang Kim
Kyoung-Jin Park
Hong-Yoep NA
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 CN201480024856.0A priority Critical patent/CN105164120B/en
Publication of WO2014185751A1 publication Critical patent/WO2014185751A1/en

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Definitions

  • the present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the organic EL device has advantages in that it can be produced at a lower cost than a device for a liquid crystal display (LCD), and it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • the organic EL device has been rapidly developed. For example, efficiency and lifespan have been improved 80 times or more and 100 times or more, respectively, compared to those of the first model. Furthermore, it is an advantage for the organic EL device to be large-sized. Recently, a 40-inch panel for the organic EL device was released.
  • lifespan and luminous efficiency need to be improved. In order to improve lifespan, the materials must be prevented from being crystallized due to Joule heat during an operation of the device. Therefore, it is necessary to develop organic compounds that have good electron injecting and transporting abilities and high electro-chemical stability.
  • the most important factor determining luminous efficiency in the organic EL device is light-emitting materials.
  • fluorescent materials have been widely used as light-emitting materials.
  • phosphorescent light-emitting materials are widely being researched.
  • a host/dopant system can be employed as the light-emitting material. Where just one compound is employed to form a light-emitting layer, maximum luminous wavelength can be shifted to be longer, color purity can be degraded, and efficiencies can be decreased due to quenching.
  • the host/dopant system is advantageous to improve color purity, luminous efficiency and stability.
  • 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)picolinate iridium (Firpic) as red-, green- and blue-emitting materials, respectively.
  • 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent materials.
  • the organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Furthermore, the operational lifespan of the organic EL device is short, and luminous efficiency is still required in order to be improved.
  • Electron transport materials act to transport electrons injected from cathode to a light-emitting layer and to increase recombination opportunities between electrons and holes by inhibiting migration of holes that failed to be combined with electrons in a light-emitting layer.
  • Compounds which have electron-withdrawing moieties to stabilize anion radical or metal complexes which can accept electrons well have been generally used as the electron transport materials.
  • conventional electron transport materials include aluminum complexes such as tris(8-hydroxyquinolinato)aluminum(III) (Alq 3 ) which have been employed before being introduced the multi-layered thin OLED by Kodak in 1987, and beryllium complexes such as bis(10-hydroxybenzo[h]quinolinato)beryllium [Be(bq) 2 ] which was introduced in Japan in mid-1990s [T. Sato et.al. J. Mater.Chem. 10 (2000) 1151].
  • Alq 3 tris(8-hydroxyquinolinato)aluminum(III)
  • Be(bq) 2 bis(10-hydroxybenzo[h]quinolinato)beryllium
  • Non-metal complex types of electron transport materials include 2,2’-bis(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)-9,9’-spirobifluorene (Spiro-PBD) [N. Johansson et.al.Adv. Mater. 10 (1998) 1136], PyPySPyPy [M. Uchida et.al. Chem. Mater. 13 (2001) 2680], and 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) of Kodak [Y.-T. Tao et.al. Appl. Phys. Lett. 77 (2000) 1575].
  • Spiro-PBD 2,2’-bis(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)-9,9’-spirobifluorene
  • Spiro-PBD 2,2’
  • Korean Patent Appln. Laying-Open No. 10-2012-0060611 discloses compounds for an organic electroluminescent device in which fluorene moiety in spirofluorene-benzothiophene fused backbone is substituted with nitrogen-containing heteroaryl.
  • organic electroluminescent compounds in which the moiety which is directly fused with another structure such as benzothiophene is substituted with aryl, heteroaryl, etc.
  • OLED cannot show good luminous and power efficiencies; and the prior art fails to suggest that the compounds can be employed as an electron transport material.
  • the objective of the present invention is to provide an organic electroluminescent compound, which can provide an organic electroluminescent device showing excellent luminous and power effeiciencies.
  • X represents -O-, -S-, -CR 11 R 12 -, -NR 13 -, or -SiR 14 R 15 -;
  • T 1 represents -(L 1 ) d -(A 1 ) e ,
  • T 2 represents -(L 2 ) f -(A 2 ) g , provided that both T 1 and T 2 are not hydrogen, simultaneously;
  • L 1 and L 2 each independently, represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
  • a 1 and A 2 each independently, represent hydrogen, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl, -NR 16 R 17 , or -SiR 18 R 19 R 20 ;
  • an organic electroluminescent device showing excellent luminous and power effeiciencies can be provided.
  • the present invention provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
  • the compound of formula 1 of the present invention is as follows.
  • alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • Alkenyl includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • Alkynyl includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • “Cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • aryl(ene) indicates a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, 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.
  • the substituents for the substituted groups of L 1 , L 2 , A 1 , A 2 , R 1 to R 3 , and R 11 to R 20 of formula 1, each independently, are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen; a (C1-C30)alkoxy; a (C6-C30)aryl; a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl; a (C3-C30)cycloalkyl; a (5- to 7-membered)heterocycloalkyl; a tri(
  • X represents -O-, -S-, -CR 11 R 12 -, -NR 13 -, or -SiR 14 R 15 -.
  • T 1 represents -(L 1 ) d -(A 1 ) e
  • T 2 represents -(L 2 ) f -(A 2 ) g , provided that both T 1 and T 2 are not hydrogen, simultaneously.
  • L 1 and L 2 each independently, represent, preferably, a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene. More preferably, L 1 and L 2 , each independently, represent a single bond; a (C6-C20)arylene unsubstituted or substituted with a (C1-C10)alkyl; or a (5- to 20-membered)heteroarylene unsubstituted or substituted with a (C1-C10)alkyl.
  • a 1 and A 2 each independently, represent, preferably, hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered) heteroaryl; and more preferably, hydrogen; a (C6-C20)aryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12)cycloalkyl or a (C6-C18)aryl; or a nitrogen-containing (5- to 20-membered)heteroaryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12)cycloalkyl or a (C6-C18)aryl.
  • a 1 and A 2 each independently, may represent a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted triazine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted quinoline, a substituted or unsubstituted quinazoline, a substituted or unsubstituted quinoxaline, or a substituted or unsubstituted naphthyridine.
  • R 1 and R 3 each independently, represent preferably, hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino,
  • R 1 and R 3 represent hydrogen, and R 2 represents hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and even more preferably, R 1 and R 3 represent hydrogen, and R 2 represents hydrogen, or a substituted or unsubstituted (C6-C20)aryl.
  • R 11 to R 20 each independently, represent a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl, or may be linked to an adjacent substituent(s) to form a (5- to 20-membered), mono- or polycyclic, alicyclic or aromatic ring; and more preferably, a (C1-C10)alkyl or a (C6-C20)aryl, or may be linked to an adjacent substituent(s) to form a (5- to 20-membered) monocyclic alicyclic ring.
  • L 1 and L 2 each independently, represent a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene;
  • a 1 and A 2 each independently, represent hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl;
  • R 1 and R 3 represent hydrogen;
  • R 2 represents hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl;
  • R 11 to R 20 each independently, represent a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a
  • L 1 and L 2 each independently, represent a single bond; a (C6-C20)arylene unsubstituted or substituted with a (C1-C10)alkyl; or a (5- to 20-membered)heteroarylene unsubstituted or substituted with a (C1-C10)alkyl;
  • a 1 and A 2 each independently, represent hydrogen; a (C6-C20)aryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12)cycloalkyl or a (C6-C18)aryl; or a nitrogen-containing (5- to 20-membered)heteroaryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12
  • organic electroluminescent compounds of formula 1 of the present invention include the following, but are not limited thereto:
  • organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1 to 3.
  • reaction scheme 1 to 3 X, T 1 , T 2 , R 1 to R 3 , and a to c are as defined in formula 1 above, and Hal represents a halogen.
  • the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the material may consist of the organic electroluminescent compound of formula 1. Otherwise, the material may further comprise a conventional compound(s) which has been comprised of an organic electroluminescent material, in addition to the compound of formula 1.
  • the organic electroluminescent device may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise at least one compound of formula 1.
  • the organic layer may comprise a light-emitting layer, or a light-emitting layer and an electron transport layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an interlayer, a buffer layer, a hole blocking layer, and an electron blocking layer.
  • the compound of the present invention may be comprised in the electron transport layer or the light-emitting layer.
  • it When used in the electron transport layer, it may be comprised as an electron transport material.
  • it When used in the light-emitting layer, it may be comprised as a host material.
  • the light-emitting layer may further comprise at least one dopant, and if needed, a compound other than the compound of the present invention may be comprised additionally as a second host material.
  • the second host material may be from any of the known phosphorescent host materials. Specifically, the material selected from the group consisting of the compounds of formulae 3 to 7 below is preferable as the second host material in view of luminous 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, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered) heteroaryl or R 25 R 26 R 27 Si-;
  • R 25 to R 27 each independently, represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
  • M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted
  • the second host material includes the following:
  • the dopant for the organic electroluminescent device of the present invention includes compounds represented by the following formulae 8 to 10.
  • L is selected from the following:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 and R 111 to R 123 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy; or R 120 to R 123 may be linked with an adjacent substituent(s) to form a fused ring, e.g.
  • R 124 to R 127 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where R 124 to R 127 are aryl, they may be linked with an adjacent substituent(s) to form a fused ring, e.g.
  • R 201 to R 211 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, or a substituted or unsubstituted (C3-C30)cycloalkyl; o and p, each independently, represent an integer of 1 to 3; where o or p is an integer of 2 or more, each of R 100 may be the same or different; and n represents an integer of 1 to 3.
  • the dopant materials include the following:
  • the present invention provides a mixture or composition for preparing an organic electroluminescent device.
  • the mixture or composition comprises the compound of the present invention.
  • the mixture or composition may further comprise a conventional compound(s) for preparing an organic electroluminescent device, in addition to the compound of formula 1.
  • the mixture or composition may be one for preparing a light-emitting layer or an electron transport layer of an organic electroluminescent device.
  • the compound of the present invention may be comprised as a host material.
  • the compound of the present invention may be comprised as an electron transport material.
  • the mixture or composition may further comprise a second host material, in which the ratio of the first host material to the second host material may be in the range of 1:99 to 99:1.
  • the second host material may be any known host material, and preferably may be selected from the group consisting of the compounds of formulae 3 to 7 above, in view of luminous efficiency.
  • the organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise a light-emitting layer, which may comprise the composition for the organic electroluminescent device of the present invention.
  • the organic electroluminescent device of the present invention may further comprise, in addition to the compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • the organic layer may further comprise 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 known in the field, besides the compound of the present invention. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
  • at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound of the present invention. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
  • a surface layer may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer.
  • a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds
  • the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
  • each layer of the organic electroluminescent device of the present invention dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
  • a wet film-forming method a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • the reaction was completed by the addition of ammonium chloride aqueous solution to the reaction mixture, and the mixture was then extracted with ethyl acetate.
  • the obtained organic layer was dried with magnesium sulfate, and the solvent was removed therefrom with a rotary evaporator.
  • Acetic acid 110 mL and HCl 11 mL were added to the obtained compound 1-3, and the mixture was then stirred overnight at 120°C. After removing the solvent with a rotary evaporator, the remaining products were purified by a column chromatography to obtain compound 1-4 (7.5 g, 61 %).
  • Compound 4-2 (28.27 g, 79 %) was obtained in the same manner as in the preparation of compound 1-2 by using compound 4-1 (26 g, 88.4 mmol), paratoluene sulphonic acid (52 g, 265.86 mmol), sodium nitrite (13 g, 177.33 mmol), and potassium iodide (36.45 g, 221.34 mmol).
  • Compound 4-3 was obtained in the same manner as in the preparation of compound 1-3, by using compound 4-2 (28.27 g, 69.86 mmol) tetrahydrofuran 200 mL, n-butyl lithium (37.2 mL, 2.5 M, 90.84 mmol), and a solution of fluorenone (16.3 g, 90.83 mmol) in 260 mL tetrahydrofuran.
  • Compound 4-4 (16.7 g, 54 %) was then obtained in the same manner as in the preparation of compound 1-4 by using acetic acid 670 mL and HCl 67 mL.
  • OLED was produced using the compound of the present invention as follows.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) (Samsung Corning) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1’ -([1,1’-biphenyl]-4,4’-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a 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 then introduced into another cell of said vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • compound H-2 of the present invention was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates, so that the dopant was deposited in a doping amount of 15 wt% based on the total amount 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(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[ d ]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell.
  • the two materials were evaporated at the same rate, so that they 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 then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • An OLED was produced. All the materials used for producing the OLED were those purified by vacuum sublimation at 10 -6 torr. The produced OLED showed green emission having a luminance of 1,330 cd/m 2 and a current density of 3.16 mA/cm 2 at a voltage of 3.1 V.
  • OLED was produced in the same manner as in Device Example 1, except for using compound H-81 as a host material and compound D-1 as a dopant to form a light-emitting layer.
  • the produced OLED showed green emission having a luminance of 980 cd/m 2 and a current density of 2.44 mA/cm 2 at a voltage of 2.54 V.
  • OLED was produced in the same manner as in Device Example 1, except for using compound B-1 as a host and compound B-2 as a dopant in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer; and using compound H-3 of the present invention as an electron transport material.
  • the produced OLED showed blue emission having a luminance of 1,020 cd/m 2 and a current density of 14.4 mA/cm 2 at a voltage of 4.2 V.
  • OLED was produced in the same manner as in Device Example 3, except for using compound H-90 of the present invention as an electron transport material.
  • the produced OLED showed blue emission having a luminance of 980 cd/m 2 and a current density of 12.4 mA/cm 2 at a voltage of 4.1 V.
  • OLED was produced in the same manner as in Device Example 1, except for using compound A-1 shown below as a host and compound D-1 as a dopant to form a light-emitting layer.
  • the produced OLED showed green emission having a luminance of 2,280 cd/m 2 and a current density of 10.65 mA/cm 2 at a driving voltage of 3.22 V.
  • an organic electroluminescent device can show excellent luminous and power efficiencies by using the compound of the present invention as a host material or an electron transport material.

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Abstract

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. By using the organic electroluminescent compound of the present invention, an organic electroluminescent device showing excellent luminous and power effeiciencies can be provided.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The organic EL device has advantages in that it can be produced at a lower cost than a device for a liquid crystal display (LCD), and it provides a wider viewing angle, a greater contrast ratio, and a faster response time. The organic EL device has been rapidly developed. For example, efficiency and lifespan have been improved 80 times or more and 100 times or more, respectively, compared to those of the first model. Furthermore, it is an advantage for the organic EL device to be large-sized. Recently, a 40-inch panel for the organic EL device was released. However, for an industrial production of the large-sized organic EL device, lifespan and luminous efficiency need to be improved. In order to improve lifespan, the materials must be prevented from being crystallized due to Joule heat during an operation of the device. Therefore, it is necessary to develop organic compounds that have good electron injecting and transporting abilities and high electro-chemical stability.
The most important factor determining luminous efficiency in the organic EL device is light-emitting materials. Until now, fluorescent materials have been widely used as light-emitting materials. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials are widely being researched. As the light-emitting material, a host/dopant system can be employed. Where just one compound is employed to form a light-emitting layer, maximum luminous wavelength can be shifted to be longer, color purity can be degraded, and efficiencies can be decreased due to quenching. The host/dopant system is advantageous to improve color purity, luminous efficiency and stability. 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)picolinate iridium (Firpic) as red-, green- and blue-emitting materials, respectively. At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent materials. Recently, Pioneer (Japan) et al., developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc., as host materials, which were known as hole blocking materials. Although conventional materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of the organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although the organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Furthermore, the operational lifespan of the organic EL device is short, and luminous efficiency is still required in order to be improved.
Electron transport materials act to transport electrons injected from cathode to a light-emitting layer and to increase recombination opportunities between electrons and holes by inhibiting migration of holes that failed to be combined with electrons in a light-emitting layer. Compounds which have electron-withdrawing moieties to stabilize anion radical or metal complexes which can accept electrons well have been generally used as the electron transport materials. Representative examples of conventional electron transport materials include aluminum complexes such as tris(8-hydroxyquinolinato)aluminum(III) (Alq3) which have been employed before being introduced the multi-layered thin OLED by Kodak in 1987, and beryllium complexes such as bis(10-hydroxybenzo[h]quinolinato)beryllium [Be(bq)2] which was introduced in Japan in mid-1990s [T. Sato et.al. J. Mater.Chem. 10 (2000) 1151]. OLED started to be commercialized in 2002. Since then, it was appeared that these materials have limits, and thus high-performance electron transport materials have been studied and reported for commercialization of OLED. Non-metal complex types of electron transport materials include 2,2’-bis(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)-9,9’-spirobifluorene (Spiro-PBD) [N. Johansson et.al.Adv. Mater. 10 (1998) 1136], PyPySPyPy [M. Uchida et.al. Chem. Mater. 13 (2001) 2680], and 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) of Kodak [Y.-T. Tao et.al. Appl. Phys. Lett. 77 (2000) 1575]. However, they also need to be improved in luminous features and lifespan. The conventional electron transport materials which have been reported to be improved show worse actual voltage and lifespan than those expected; there is a big deviation of lifespan among RGB; and they have poor thermal stability. Due to these problems, it is difficult for power consumption and luminance to be improved, which are obstacles for the production of large-sized OLED panels.
Korean Patent Appln. Laying-Open No. 10-2012-0060611 discloses compounds for an organic electroluminescent device in which fluorene moiety in spirofluorene-benzothiophene fused backbone is substituted with nitrogen-containing heteroaryl. However, it fails to disclose organic electroluminescent compounds in which the moiety which is directly fused with another structure such as benzothiophene is substituted with aryl, heteroaryl, etc. Furthermore, where the compounds of the prior art are employed as a host, OLED cannot show good luminous and power efficiencies; and the prior art fails to suggest that the compounds can be employed as an electron transport material.
The objective of the present invention is to provide an organic electroluminescent compound, which can provide an organic electroluminescent device showing excellent luminous and power effeiciencies.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2014004424-appb-I000001
wherein, X represents -O-, -S-, -CR11R12-, -NR13-, or -SiR14R15-; T1 represents -(L1)d-(A1)e, T2 represents -(L2)f-(A2)g, provided that both T1 and T2 are not hydrogen, simultaneously; L1 and L2, each independently, represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene; A1 and A2, each independently, represent hydrogen, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl, -NR16R17, or -SiR18R19R20; R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; R11 to R20, each independently, represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; a and c, each independently, represent an integer of 1 to 4; b represents an integer of 1 or 2; where a to c is 2 or more, each of R1 to R3 may be the same or different; d to g, each independently, represent an integer of 1 to 3; where d to g is 2 or more, each of L1, A1, L2 and A2 may be the same or different; and the heteroarylene and heteroaryl, each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
By using the organic electroluminescent compound of the present invention, an organic electroluminescent device showing excellent luminous and power effeiciencies can be provided.
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 provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
The compound of formula 1 of the present invention is as follows.
Specifically, the compound of formula 1 is represented by the following formula 2:
Figure PCTKR2014004424-appb-I000002
wherein, X, T1, T2, R1 to R3, and a to c are as defined in formula 1 above.
Herein, “alkyl” includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “Alkenyl” includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “Alkynyl” includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. “Cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “(5- to 7-membered) heterocycloalkyl” indicates a cycloalkyl having 5 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, P(=O), Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. Furthermore, “aryl(ene)” indicates a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “(3- to 30-membered) heteroaryl(ene)” indicates an aryl group having 3 to 30 ring backbone atoms including at least one, preferably 1 to 4, hetero atom selected from the group consisting of B, N, O, S, P(=O), Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl such as 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 such as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, etc. Furthermore, “halogen” includes F, Cl, Br, and I.
Herein, “substituted” in the expression, “substituted or unsubstituted,” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e. a substituent. The substituents for the substituted groups of L1, L2, A1, A2, R1 to R3, and R11 to R20 of formula 1, each independently, are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen; a (C1-C30)alkoxy; a (C6-C30)aryl; a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl; a (C3-C30)cycloalkyl; a (5- to 7-membered)heterocycloalkyl; a tri(C1-C30)alkylsilyl; a tri(C6-C30)arylsilyl; a di(C1-C30)alkyl(C6-C30)arylsilyl; a (C1-C30)alkyldi(C6-C30)arylsilyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a cyano; a di(C1-C30)alkylamino; a di(C6-C30)arylamino; a (C1-C30)alkyl(C6-C30)arylamino; a di(C6-C30)arylboronyl; a di(C1-C30)alkylboronyl; a (C1-C30)alkyl(C6-C30)arylboronyl; a (C6-C30)aryl(C1-C30)alkyl; a (C1-C30)alkyl(C6-C30)aryl; a carboxy; a nitro; and a hydroxyl; or preferably, each independently, are at least one selected from the group consisting of deuterium; a halogen; a (C1-C6)alkyl; a (C6-C12)aryl; a (5- to 30-membered)heteroaryl; a (C3-C30)cycloalkyl; and a cyano.
In formula 1, X represents -O-, -S-, -CR11R12-, -NR13-, or -SiR14R15-.
In formula 1, T1 represents -(L1)d-(A1)e, and T2 represents -(L2)f-(A2)g, provided that both T1 and T2 are not hydrogen, simultaneously.
In formula 1, L1 and L2, each independently, represent, preferably, a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene. More preferably, L1 and L2, each independently, represent a single bond; a (C6-C20)arylene unsubstituted or substituted with a (C1-C10)alkyl; or a (5- to 20-membered)heteroarylene unsubstituted or substituted with a (C1-C10)alkyl.
In formula 1, A1 and A2, each independently, represent, preferably, hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered) heteroaryl; and more preferably, hydrogen; a (C6-C20)aryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12)cycloalkyl or a (C6-C18)aryl; or a nitrogen-containing (5- to 20-membered)heteroaryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12)cycloalkyl or a (C6-C18)aryl. Specifically, A1 and A2, each independently, may represent a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted triazine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted quinoline, a substituted or unsubstituted quinazoline, a substituted or unsubstituted quinoxaline, or a substituted or unsubstituted naphthyridine.
In formula 1, R1 and R3, each independently, represent preferably, hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and R2 represents preferably, hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur. More preferably, R1 and R3 represent hydrogen, and R2 represents hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and even more preferably, R1 and R3 represent hydrogen, and R2 represents hydrogen, or a substituted or unsubstituted (C6-C20)aryl.
Preferably, R11 to R20, each independently, represent a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl, or may be linked to an adjacent substituent(s) to form a (5- to 20-membered), mono- or polycyclic, alicyclic or aromatic ring; and more preferably, a (C1-C10)alkyl or a (C6-C20)aryl, or may be linked to an adjacent substituent(s) to form a (5- to 20-membered) monocyclic alicyclic ring.
According to one embodiment of the present invention, in formula 1, L1 and L2, each independently, represent a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene; A1 and A2, each independently, represent hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; R1 and R3 represent hydrogen; R2 represents hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and R11 to R20, each independently, represent a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl, or may be linked to an adjacent substituent(s) to form a (5- to 20-membered), mono- or polycyclic, alicyclic or aromatic ring.
According to another embodiment of the present invention, in formula 1, L1 and L2, each independently, represent a single bond; a (C6-C20)arylene unsubstituted or substituted with a (C1-C10)alkyl; or a (5- to 20-membered)heteroarylene unsubstituted or substituted with a (C1-C10)alkyl; A1 and A2, each independently, represent hydrogen; a (C6-C20)aryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12)cycloalkyl or a (C6-C18)aryl; or a nitrogen-containing (5- to 20-membered)heteroaryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12)cycloalkyl or a (C6-C18)aryl; R1 and R3 represent hydrogen; R2 represents hydrogen, or a substituted or unsubstituted (C6-C20)aryl; and R11 to R20, each independently, represent a (C1-C10)alkyl or a (C6-C20)aryl; or may be linked to an adjacent substituent(s) to form a (5- to 20-membered) monocyclic aliphatic ring.
More specifically, organic electroluminescent compounds of formula 1 of the present invention include the following, but are not limited thereto:
Figure PCTKR2014004424-appb-I000003
Figure PCTKR2014004424-appb-I000004
Figure PCTKR2014004424-appb-I000005
Figure PCTKR2014004424-appb-I000006
Figure PCTKR2014004424-appb-I000007
Figure PCTKR2014004424-appb-I000008
Figure PCTKR2014004424-appb-I000009
Figure PCTKR2014004424-appb-I000010
Figure PCTKR2014004424-appb-I000011
Figure PCTKR2014004424-appb-I000012
Figure PCTKR2014004424-appb-I000013
Figure PCTKR2014004424-appb-I000014
Figure PCTKR2014004424-appb-I000015
Figure PCTKR2014004424-appb-I000016
Figure PCTKR2014004424-appb-I000017
Figure PCTKR2014004424-appb-I000018
Figure PCTKR2014004424-appb-I000019
Figure PCTKR2014004424-appb-I000020
Figure PCTKR2014004424-appb-I000021
Figure PCTKR2014004424-appb-I000022
Figure PCTKR2014004424-appb-I000023
Figure PCTKR2014004424-appb-I000024
Figure PCTKR2014004424-appb-I000025
Figure PCTKR2014004424-appb-I000026
Figure PCTKR2014004424-appb-I000027
Figure PCTKR2014004424-appb-I000028
Figure PCTKR2014004424-appb-I000029
Figure PCTKR2014004424-appb-I000030
Figure PCTKR2014004424-appb-I000031
Figure PCTKR2014004424-appb-I000032
Figure PCTKR2014004424-appb-I000033
Figure PCTKR2014004424-appb-I000034
Figure PCTKR2014004424-appb-I000035
Figure PCTKR2014004424-appb-I000036
Figure PCTKR2014004424-appb-I000037
Figure PCTKR2014004424-appb-I000038
Figure PCTKR2014004424-appb-I000039
Figure PCTKR2014004424-appb-I000040
Figure PCTKR2014004424-appb-I000041
Figure PCTKR2014004424-appb-I000042
Figure PCTKR2014004424-appb-I000043
Figure PCTKR2014004424-appb-I000044
Figure PCTKR2014004424-appb-I000045
Figure PCTKR2014004424-appb-I000046
Figure PCTKR2014004424-appb-I000047
Figure PCTKR2014004424-appb-I000048
Figure PCTKR2014004424-appb-I000049
Figure PCTKR2014004424-appb-I000050
Figure PCTKR2014004424-appb-I000051
Figure PCTKR2014004424-appb-I000052
Figure PCTKR2014004424-appb-I000053
Figure PCTKR2014004424-appb-I000054
Figure PCTKR2014004424-appb-I000055
Figure PCTKR2014004424-appb-I000056
Figure PCTKR2014004424-appb-I000057
Figure PCTKR2014004424-appb-I000058
Figure PCTKR2014004424-appb-I000059
Figure PCTKR2014004424-appb-I000060
Figure PCTKR2014004424-appb-I000061
The organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1 to 3.
[Reaction Scheme 1]
Figure PCTKR2014004424-appb-I000062
[Reaction Scheme 2]
Figure PCTKR2014004424-appb-I000063
[Reaction Scheme 3]
Figure PCTKR2014004424-appb-I000064
In reaction scheme 1 to 3, X, T1, T2, R1 to R3, and a to c are as defined in formula 1 above, and Hal represents a halogen.
According to another aspect of the present invention, the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material. The material may consist of the organic electroluminescent compound of formula 1. Otherwise, the material may further comprise a conventional compound(s) which has been comprised of an organic electroluminescent material, in addition to the compound of formula 1.
The organic electroluminescent device may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise at least one compound of formula 1.
One of the first and second electrodes may be an anode, and the other may be a cathode. The organic layer may comprise a light-emitting layer, or a light-emitting layer and an electron transport layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an interlayer, a buffer layer, a hole blocking layer, and an electron blocking layer.
The compound of the present invention may be comprised in the electron transport layer or the light-emitting layer. When used in the electron transport layer, it may be comprised as an electron transport material. When used in the light-emitting layer, it may be comprised as a host material. Preferably, the light-emitting layer may further comprise at least one dopant, and if needed, a compound other than the compound of the present invention may be comprised additionally as a second host material. The second host material may be from any of the known phosphorescent host materials. Specifically, the material selected from the group consisting of the compounds of formulae 3 to 7 below is preferable as the second host material in view of luminous efficiency.
Figure PCTKR2014004424-appb-I000065
Figure PCTKR2014004424-appb-I000066
Figure PCTKR2014004424-appb-I000067
Figure PCTKR2014004424-appb-I000068
Figure PCTKR2014004424-appb-I000069
Wherein, Cz represents the following structure:
Figure PCTKR2014004424-appb-I000070
X' represents -O- or -S-; R21 to R24, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered) heteroaryl or R25R26R27Si-; R25 to R27, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; Y1 and Y2, each independently, represent -O-, -S-, -N(R31)-, or -C(R32)(R33)-, provided that Y1 and Y2 do not simultaneously exist; R31 to R33, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; 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; and where h, i, j, k, l or m is an integer of 2 or more, each of (Cz-L4), (Cz), R21, R22, R23 or R24 may be the same or different.
Specifically, the second host material includes the following:
Figure PCTKR2014004424-appb-I000071
Figure PCTKR2014004424-appb-I000072
Figure PCTKR2014004424-appb-I000073
Figure PCTKR2014004424-appb-I000074
Figure PCTKR2014004424-appb-I000075
Figure PCTKR2014004424-appb-I000076
Figure PCTKR2014004424-appb-I000077
Figure PCTKR2014004424-appb-I000078
Figure PCTKR2014004424-appb-I000079
Figure PCTKR2014004424-appb-I000080
Figure PCTKR2014004424-appb-I000081
Figure PCTKR2014004424-appb-I000082
Figure PCTKR2014004424-appb-I000083
The dopant for the organic electroluminescent device of the present invention includes compounds represented by the following formulae 8 to 10.
Figure PCTKR2014004424-appb-I000084
wherein L is selected from the following:
Figure PCTKR2014004424-appb-I000085
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; R101 to R109 and R111 to R123, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy; or R120 to R123 may be linked with an adjacent substituent(s) to form a fused ring, e.g. quinoline; R124 to R127, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where R124 to R127 are aryl, they may be linked with an adjacent substituent(s) to form a fused ring, e.g. fluorene; R201 to R211, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, or a substituted or unsubstituted (C3-C30)cycloalkyl; o and p, each independently, represent an integer of 1 to 3; where o or p is an integer of 2 or more, each of R100 may be the same or different; and n represents an integer of 1 to 3.
Specifically, the dopant materials include the following:
Figure PCTKR2014004424-appb-I000086
Figure PCTKR2014004424-appb-I000087
Figure PCTKR2014004424-appb-I000088
Figure PCTKR2014004424-appb-I000089
Figure PCTKR2014004424-appb-I000090
Figure PCTKR2014004424-appb-I000091
Figure PCTKR2014004424-appb-I000092
Figure PCTKR2014004424-appb-I000093
Figure PCTKR2014004424-appb-I000094
Figure PCTKR2014004424-appb-I000095
Figure PCTKR2014004424-appb-I000096
Figure PCTKR2014004424-appb-I000097
Figure PCTKR2014004424-appb-I000098
Figure PCTKR2014004424-appb-I000099
Figure PCTKR2014004424-appb-I000100
Figure PCTKR2014004424-appb-I000101
Furthermore, the present invention provides a mixture or composition for preparing an organic electroluminescent device. The mixture or composition comprises the compound of the present invention. The mixture or composition may further comprise a conventional compound(s) for preparing an organic electroluminescent device, in addition to the compound of formula 1. The mixture or composition may be one for preparing a light-emitting layer or an electron transport layer of an organic electroluminescent device. When the mixture or composition of the present invention is used for preparing the light-emitting layer, the compound of the present invention may be comprised as a host material. When the mixture or composition of the present invention is used for preparing the electron transport layer, the compound of the present invention may be comprised as an electron transport material. When the compound of the present invention is comprised as a host material in the mixture or composition, the mixture or composition may further comprise a second host material, in which the ratio of the first host material to the second host material may be in the range of 1:99 to 99:1. The second host material may be any known host material, and preferably may be selected from the group consisting of the compounds of formulae 3 to 7 above, in view of luminous efficiency.
The organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise a light-emitting layer, which may comprise the composition for the organic electroluminescent device of the present invention.
The organic electroluminescent device of the present invention may further comprise, in addition to the compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present invention, the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal. The organic layer may further comprise 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 known in the field, besides the compound of the present invention. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
In the organic electroluminescent device of the present invention, preferably, at least one layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device of the present 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 an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds, and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present invention, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used. When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the compound of the present invention, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound H-2
Figure PCTKR2014004424-appb-I000102
Preparation of compound 1-1
After introducing 2-bromo-5-chloroaniline (24 g, 117 mmol), 4-dibenzothiophene boronic acid (21 g, 90 mmol), tetrakis(triphenylphosphine)palladium (3.1 g, 2.7 mmol), sodium carbonate (24 g, 225 mmol), toluene 450 mL and ethanol 35 mL into a reaction vessel, distilled water 110 mL was added thereto, and the mixture was then stirred for 3 hours at 120°C. After completing the reaction, the mixture was washed with distilled water and extracted with ethyl acetate (EA). The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom using a rotary evaporator, and the remaining product was purified by a column chromatography to obtain compound 1-1 (19 g, 65 %).
Preparation of compound 1-2
After dissolving compound 1-1 (19 g, 60 mmol) and paratoluene sulphonic acid (34 g, 180 mmol) in acetonitrile of a reaction vessel, sodium nitrite (8.2 g, 120 mmol) and potassium iodide (25 g, 150 mmol) dissolved in water 380 mL were added thereto at 0°C. After stirring for 6 hours, the mixture was washed with distilled water and extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom using a rotary evaporator, and the remaining product was purified by a column chromatography to obtain compound 1-2 (18 g, 73 %).
Preparation of compound 1-4
After introducing compound 1-2 (18.2 g, 43.3 mmol) and tetrahydrofuran 200 mL to a reaction vessel, the mixture was subjected to a nitrogen purging, and cooled to -78°C. N-butyl lithium (22.5 mL, 2.5 M, 56.2 mmol) was added slowly and dropwise to the mixture. After stirring the mixture for 1 hour at -78°C, fluorenone (10.2 g, 56.6 mmol) solution in tetrahydrofuran 200 mL was added slowly and dropwise thereto. After completing the dropwise addition, the mixture was slowly warmed to room temperature, and then stirred for 30 minutes. The reaction was completed by the addition of ammonium chloride aqueous solution to the reaction mixture, and the mixture was then extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate, and the solvent was removed therefrom with a rotary evaporator. Acetic acid 110 mL and HCl 11 mL were added to the obtained compound 1-3, and the mixture was then stirred overnight at 120°C. After removing the solvent with a rotary evaporator, the remaining products were purified by a column chromatography to obtain compound 1-4 (7.5 g, 61 %).
Preparation of compound 1-5
After introducing compound 1-4 (6.0 g, 13 mmol), bis(pinacolato)diboron (4.0 g, 15.8 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) (0.6 g, 0.66 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos) (0.54 g, 1.31 mmol), KOAc (3.2 g, 33 mmol) and 1,4-dioxane 70 mL into a reaction vessel, the mixture was stirred for 4 hours at 120°C. After completing the reaction, the mixture was washed with distilled water and extracted with methylene chloride (MC). The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom with a rotary evaporator, and the remaining product was purified by a column chromatography to obtain compound 1-5 (4.8 g, 66 %).
Preparation of compound H-2
After introducing compound 1-5 (6.2 g, 11.3 mmol), 2-chloro-4,5-diphenylpyrimidine (3.3 g, 12.4 mmol), Pd2(dba)3 (517 mg, 0.56 mmol), P(t-Bu)3 (0.56 mL, 1.1 mmol), Na2CO3 (2.4 g, 22.6 mmol), toluene 50 mL and H2O 12 mL into a reaction vessel, the mixture was stirred for one day at 120°C. After completing the reaction, the mixture was washed with distilled water and extracted with MC. The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom with a rotary evaporator, and the remaining product was purified by a column chromatography to obtain compound H-2 (3 g, 41 %).
mp 383°C, UV 364 nm (in toluene), PL 389 nm (in toluene), MS/EIMS 653.8
Example 2: Preparation of compound H-3
Figure PCTKR2014004424-appb-I000103
After introducing compound 1-5 (4.4 g, 8 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.3 g, 8.4 mmol), tetrakis(triphenylphosphine)palladium (0.46 g, 0.4 mmol), potassium carbonate (2.8 g, 20 mmol), toluene 40 mL and ethanol 6 mL into a reaction vessel and adding distilled water 10 mL thereto, the mixture was stirred for 3 hours at 120°C. After completing the reaction, the mixture was washed with distilled water and extracted with MC. The obtained organic layer was dried with magnesium sulfate, the solvent was removed therefrom with a rotary evaporator, and the remaining product was purified by a column chromatography to obtain compound H-3 (4 g, 76 %).
mp 386°C, UV 352 nm (in toluene), PL 403 nm (in toluene), MS/EIMS 654.8
Example 3: Preparation of compound H-81
Figure PCTKR2014004424-appb-I000104
Preparation of compound 3-1
After introducing dibenzo[b,d]thiophen-4-yl boronic acid (17 g, 74 mmol), 1-bromo-2-iodobenzene (25 g, 88 mmol), Pd(PPh3)4 (2.5 g, 2.2 mmol), Na2CO3 (20 g, 184 mmol), toluene 368 mL, ethanol 92 mL and H2O 92 mL into a reaction vessel, the mixture was stirred under reflux. After 4 hours to complete the reaction, the mixture was washed with distilled water, and extracted with MC. The obtained layer was dried with magnesium sulfate, and the solvent was removed therefrom with a rotary evaporator. The obtained solid was dissolved in CHCl3, and the solution was purified by a column chromatography to obtain compound 3-1 (11.4 g, 46 %).
Preparation of compound 3-2
After introducing compound 3-1 (11.4 g, 34 mmol), and tetrahydrofuran(THF) 300 mL into a reaction vessel, the mixture was cooled to -78°C, and 2.5 M n-butyl lithium (17 mL, 43 mmol) was then added thereto. The mixture was stirred for 2 hours, and 9-fluorenone (9 g, 50 mmol) was then added thereto. The mixture was stirred for 17 hours. After completing the reaction, the mixture was extracted with EA and H2O. The obtained organic layer was dried with MgSO4, and the solvent was removed therefrom with a rotary evaporator to obtain compound 3-2 (14 g, 94 %).
Preparation of compound 3-3
Compound 3-2 (15 g, 34.1 mmol), HCl 40 mL and acetic acid 250 mL were introduced into a reaction vessel, and the mixture was then stirred under reflux for 14 hours, and filtered. The obtained solids were dissolved in CHCl3 and purified by a column chromatography to obtain compound 3-3 (9.4 g, 65 %).
Preparation of compound 3-4
Compound 3-3 (6.5 g, 15 mmol) and THF 300 mL were introduced into a reaction vessel. The mixture was cooled to -78°C, and 2.5 M n-butyl lithium (22 mL, 31 mmol) was added thereto. The mixture was stirred for 2 hours at room temperature, and isopropylborate (11 mL, 46 mmol) was then added thereto. The mixture was stirred for 14 hours. After completing the reaction, the mixture was extracted with EA and H2O. The obtained organic layer was dried with MgSO4, the solvent was removed therefrom with a rotary evaporator to obtain compound 3-4 (5.8 g, 83 %).
Preparation of compound H-81
Compound 3-4 (5.6 g, 12 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.9 g, 14 mmol), Pd(PPh3)4 (416 mg, 0.3 mmol), K2CO3 (3.3 g, 24 mmol), toluene 60 mL and H2O 12 mL were introduced into a reaction vessel, and the mixture was then stirred under reflux, and filtered. The obtained solids were dissolved in CHCl3 and purified by a column chromatography to obtain compound H-81 (2.4 g, 31 %).
mp 330°C, UV 296 nm (in toluene), PL 423 nm (in toluene), MS/EIMS 654.8
Example 4: Preparation of compound H-90
Figure PCTKR2014004424-appb-I000105
Preparation of compound 4-1
Compound 4-1 (26 g, 73 %) was obtained in the same manner as in the preparation of compound 1-1, by using 2-bromo-5-chloroaniline (25 g, 121.08 mmol), 4-dibenzofuran boronic acid (27 g, 127.14 mmol), tetrakis(triphenylphosphine)palladium (28 g, 24.216 mmol), 2 M Na2CO3 180 mL, toluene 600 mL and ethanol 180 mL.
Preparation of compound 4-2
Compound 4-2 (28.27 g, 79 %) was obtained in the same manner as in the preparation of compound 1-2 by using compound 4-1 (26 g, 88.4 mmol), paratoluene sulphonic acid (52 g, 265.86 mmol), sodium nitrite (13 g, 177.33 mmol), and potassium iodide (36.45 g, 221.34 mmol).
Preparation of compound 4-4
Compound 4-3 was obtained in the same manner as in the preparation of compound 1-3, by using compound 4-2 (28.27 g, 69.86 mmol) tetrahydrofuran 200 mL, n-butyl lithium (37.2 mL, 2.5 M, 90.84 mmol), and a solution of fluorenone (16.3 g, 90.83 mmol) in 260 mL tetrahydrofuran. Compound 4-4 (16.7 g, 54 %) was then obtained in the same manner as in the preparation of compound 1-4 by using acetic acid 670 mL and HCl 67 mL.
Preparation of compound 4-5
Compound 4-4 (16.7 g, 37.88 mmol), bis(pinacolato)diboron (10.6 g, 41.66 mmol), Pd2(dba)3 (0.35 g, 0.38 mmol), potassium acetate (7.4 g, 75.76 mmol) and acetonitrile 190 mL were introduced into a reaction vessel. The mixture was then stirred under reflux for 6 hours at 120°C. After completing the reaction, the mixture was extracted with dichloromethane/purified water, and purified by a column chromatography to obtain compound 4-5 (12.5 g, 62 %).
Preparation of compound H-90
Compound H-90 (4 g, 76 %) was obtained in the same manner as in the preparation of compound H-3, by using compound 4-5 (6 g, 11.27 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3 g, 11.27 mmol), tetrakis(triphenylphosphine)palladium (1.3 g, 1.127 mmol), 2 M potassium carbonate 15 mL, toluene 60 mL and ethanol 15mL.
mp 428°C, UV 298 nm (in toluene), PL 395 nm (in toluene), MS/EIMS 638.2
Example 5: Preparation of compound H-343
Figure PCTKR2014004424-appb-I000106
Compound 4-5 (6 g, 11.27 mmol), 2-chloro-4-phenylquinazoline (2.7 g, 11.27 mmol), Pd(PPh3)4 (1.3 g, 1.127 mmol), 2 M Na2CO3 15 mL, toluene 60 mL and ethanol 15 mL were introduced into a reaction vessel, and the mixture was then stirred under reflux for 10 hours at 120°C. After completing the reaction, the mixture was washed with distilled water, and extracted with EA. The organic layer was then dried with magnesium sulfate, the solvent was removed therefrom with a rotary evaporator, and the remaining product was purified by a column chromatography to obtain compound H-343 (1.6 g, 24 %).
mp 341°C, UV 324 nm (in toluene), PL 387 nm (in toluene), MS/EIMS 611.2
[Device Example 1] OLED using the compound of the present invention
OLED was produced using the compound of the present invention as follows. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) (Samsung Corning) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1’-([1,1’-biphenyl]-4,4’-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzene-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a 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 then introduced into another cell of said vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound H-2 of the present invention was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant. The two materials were evaporated at different rates, so that the dopant was deposited in a doping amount of 15 wt% based on the total amount 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(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate, so that they 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. 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 then deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED was produced. All the materials used for producing the OLED were those purified by vacuum sublimation at 10-6 torr. The produced OLED showed green emission having a luminance of 1,330 cd/m2 and a current density of 3.16 mA/cm2 at a voltage of 3.1 V.
[Device Example 2] OLED using the compound of the present invention
OLED was produced in the same manner as in Device Example 1, except for using compound H-81 as a host material and compound D-1 as a dopant to form a light-emitting layer. The produced OLED showed green emission having a luminance of 980 cd/m2 and a current density of 2.44 mA/cm2 at a voltage of 2.54 V.
[Device Example 3] OLED using the compound of the present invention
OLED was produced in the same manner as in Device Example 1, except for using compound B-1 as a host and compound B-2 as a dopant in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer; and using compound H-3 of the present invention as an electron transport material. The produced OLED showed blue emission having a luminance of 1,020 cd/m2 and a current density of 14.4 mA/cm2 at a voltage of 4.2 V.
Figure PCTKR2014004424-appb-I000107
[Device Example 4] OLED using the compound of the present invention
OLED was produced in the same manner as in Device Example 3, except for using compound H-90 of the present invention as an electron transport material. The produced OLED showed blue emission having a luminance of 980 cd/m2 and a current density of 12.4 mA/cm2 at a voltage of 4.1 V.
[Comparative Device Example 1] OLED using conventional compounds
OLED was produced in the same manner as in Device Example 1, except for using compound A-1 shown below as a host and compound D-1 as a dopant to form a light-emitting layer. The produced OLED showed green emission having a luminance of 2,280 cd/m2 and a current density of 10.65 mA/cm2 at a driving voltage of 3.22 V.
Figure PCTKR2014004424-appb-I000108
From the above device examples, it is confirmed that an organic electroluminescent device can show excellent luminous and power efficiencies by using the compound of the present invention as a host material or an electron transport material.

Claims (9)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014004424-appb-I000109
    wherein, X represents -O-, -S-, -CR11R12-, -NR13-, or -SiR14R15-;
    T1 represents -(L1)d-(A1)e, T2 represents -(L2)f-(A2)g, provided that both T1 and T2 are not hydrogen, simultaneously;
    L1 and L2, each independently, represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
    A1 and A2, each independently, represent hydrogen, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl, -NR16R17, or -SiR18R19R20;
    R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
    R11 to R20, each independently, represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
    a and c, each independently, represent an integer of 1 to 4; b represents an integer of 1 or 2; where a to c is 2 or more, each of R1 to R3 may be the same or different; d to g, each independently, represent an integer of 1 to 3; where d to g is 2 or more, each of L1, A1, L2 and A2 may be the same or different; and
    the heteroarylene and heteroaryl, each independently, 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 compound of formula 1 is represented by the following formula 2:
    Figure PCTKR2014004424-appb-I000110
    wherein X, T1, T2, R1 to R3, and a to c are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C6-C30)arylene, the substituted (3- to 30-membered)heteroarylene of L1 and L2, the substituted (C6-C30)aryl, the substituted (5- to 30-membered)heteroaryl of A1 and A2, the substituted (C1-C30)alkyl, the substituted (C6-C30)aryl, the substituted (3- to 30-membered)heteroaryl, the substituted (C3-C30)cycloalkyl, the substituted (C1-C30)alkoxy, the substituted tri(C1-C30)alkylsilyl, the substituted di(C1-C30)alkyl(C6-C30)arylsilyl, the substituted (C1-C30)alkyldi(C6-C30)arylsilyl, the substituted tri(C6-C30)arylsilyl, the substituted mono- or di- (C1-C30)alkylamino, the substituted mono- or di- (C6-C30)arylamino, the substituted (C1-C30)alkyl(C6-C30)arylamino of R1 to R3, and the substituted (C1-C30)alkyl, the substituted (C6-C30)aryl, the substituted (3- to 30-membered)heteroaryl of R11 to R20, each independently, are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen; a (C1-C30)alkoxy; a (C6-C30)aryl; a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl; a (C3-C30)cycloalkyl; a (5- to 7-membered)heterocycloalkyl; a tri(C1-C30)alkylsilyl; a tri(C6-C30)arylsilyl; a di(C1-C30)alkyl(C6-C30)arylsilyl; a (C1-C30)alkyldi(C6-C30)arylsilyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a cyano; a di(C1-C30)alkylamino; a di(C6-C30)arylamino; a (C1-C30)alkyl(C6-C30)arylamino; a di(C6-C30)arylboronyl; a di(C1-C30)alkylboronyl; a (C1-C30)alkyl(C6-C30)arylboronyl; a (C6-C30)aryl(C1-C30)alkyl; a (C1-C30)alkyl(C6-C30)aryl; a carboxy; a nitro; and a hydroxy.
  4. The organic electroluminescent compound according to claim 1, wherein R1 and R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and
    R2 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur.
  5. The organic electroluminescent compound according to claim 1, wherein L1 and L2, each independently, represent a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene;
    A1 and A2, each independently, represent hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl;
    R1 to R3, each independently, represent hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and
    R11 to R20, each independently, represent a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl, or may be linked to an adjacent substituent(s) to form a (5- to 20-membered), mono- or polycyclic, alicyclic or aromatic ring.
  6. The organic electroluminescent compound according to claim 1, wherein L1 and L2, each independently, represent a single bond; a (C6-C20)arylene unsubstituted or substituted with a (C1-C10)alkyl; or a (5- to 20-membered)heteroarylene unsubstituted or substituted with a (C1-C10)alkyl;
    A1 and A2, each independently, represent hydrogen; a (C6-C20)aryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12)cycloalkyl or a (C6-C18)aryl; or a nitrogen-containing (5- to 20-membered)heteroaryl unsubstituted or substituted with deuterium, a halogen, a cyano, a (C1-C10)alkyl, a (C6-C12)cycloalkyl or a (C6-C18)aryl;
    R1 to R3, each independently, represent hydrogen, or a (C6-C20)aryl; and
    R11 to R20, each independently, represent a (C1-C10)alkyl or a (C6-C20)aryl; or may be linked to an adjacent substituent(s) to form a (5- to 20-membered) monocyclic aliphatic ring.
  7. The organic electroluminescent compound according to claim 1, wherein A1 and A2, each independently, represent a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted triazine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted quinoline, a substituted or unsubstituted quinazoline, a substituted or unsubstituted quinoxaline, or a substituted or unsubstituted naphthyridine.
  8. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2014004424-appb-I000111
    Figure PCTKR2014004424-appb-I000112
    Figure PCTKR2014004424-appb-I000113
    Figure PCTKR2014004424-appb-I000114
    Figure PCTKR2014004424-appb-I000115
    Figure PCTKR2014004424-appb-I000116
    Figure PCTKR2014004424-appb-I000117
    Figure PCTKR2014004424-appb-I000118
    Figure PCTKR2014004424-appb-I000119
    Figure PCTKR2014004424-appb-I000120
    Figure PCTKR2014004424-appb-I000121
    Figure PCTKR2014004424-appb-I000122
    Figure PCTKR2014004424-appb-I000123
    Figure PCTKR2014004424-appb-I000124
    Figure PCTKR2014004424-appb-I000125
    Figure PCTKR2014004424-appb-I000126
    Figure PCTKR2014004424-appb-I000127
    Figure PCTKR2014004424-appb-I000128
    Figure PCTKR2014004424-appb-I000129
    Figure PCTKR2014004424-appb-I000130
    Figure PCTKR2014004424-appb-I000131
    Figure PCTKR2014004424-appb-I000132
    Figure PCTKR2014004424-appb-I000133
    Figure PCTKR2014004424-appb-I000134
    Figure PCTKR2014004424-appb-I000135
    Figure PCTKR2014004424-appb-I000136
    Figure PCTKR2014004424-appb-I000137
    Figure PCTKR2014004424-appb-I000138
    Figure PCTKR2014004424-appb-I000139
    Figure PCTKR2014004424-appb-I000140
    Figure PCTKR2014004424-appb-I000141
    Figure PCTKR2014004424-appb-I000142
    Figure PCTKR2014004424-appb-I000143
    Figure PCTKR2014004424-appb-I000144
    Figure PCTKR2014004424-appb-I000145
    Figure PCTKR2014004424-appb-I000146
    Figure PCTKR2014004424-appb-I000147
    Figure PCTKR2014004424-appb-I000148
    Figure PCTKR2014004424-appb-I000149
    Figure PCTKR2014004424-appb-I000150
    Figure PCTKR2014004424-appb-I000151
    Figure PCTKR2014004424-appb-I000152
    Figure PCTKR2014004424-appb-I000153
    Figure PCTKR2014004424-appb-I000154
    Figure PCTKR2014004424-appb-I000155
    Figure PCTKR2014004424-appb-I000156
    Figure PCTKR2014004424-appb-I000157
    Figure PCTKR2014004424-appb-I000158
    Figure PCTKR2014004424-appb-I000159
    Figure PCTKR2014004424-appb-I000160
    Figure PCTKR2014004424-appb-I000161
    Figure PCTKR2014004424-appb-I000162
    Figure PCTKR2014004424-appb-I000163
    Figure PCTKR2014004424-appb-I000164
    Figure PCTKR2014004424-appb-I000165
    Figure PCTKR2014004424-appb-I000166
    Figure PCTKR2014004424-appb-I000167
    Figure PCTKR2014004424-appb-I000168
    Figure PCTKR2014004424-appb-I000169
  9. An organic electroluminescent device comprising the compound according to claim 1.
PCT/KR2014/004424 2013-05-16 2014-05-16 Organic electroluminescent compounds and organic electroluminescent device comprising the same WO2014185751A1 (en)

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US20160218300A1 (en) * 2015-01-25 2016-07-28 Universal Display Corporation Organic Electroluminescent Materials and Devices
JP2018507174A (en) * 2014-12-24 2018-03-15 ドゥーサン コーポレイション Organic compound and organic electroluminescent device including the same
US20180166638A1 (en) * 2015-06-12 2018-06-14 Sfc Co., Ltd. Organic light-emitting diode with high efficiency
CN108349922A (en) * 2015-11-12 2018-07-31 Sfc株式会社 Novel organic luminescent compounds and organic illuminating element including this
JP2018535185A (en) * 2016-02-25 2018-11-29 エルジー・ケム・リミテッド Heterocyclic compound and organic light emitting device including the same
US10355222B2 (en) 2015-02-06 2019-07-16 Universal Display Corporation Organic electroluminescent materials and devices
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