WO2015099485A1 - An organic electroluminescent compound and an organic electroluminescent device comprising the same - Google Patents

An organic electroluminescent compound and an organic electroluminescent device comprising the same Download PDF

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WO2015099485A1
WO2015099485A1 PCT/KR2014/012893 KR2014012893W WO2015099485A1 WO 2015099485 A1 WO2015099485 A1 WO 2015099485A1 KR 2014012893 W KR2014012893 W KR 2014012893W WO 2015099485 A1 WO2015099485 A1 WO 2015099485A1
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unsubstituted
substituted
aryl
alkyl
membered
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PCT/KR2014/012893
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French (fr)
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Hee-Choon Ahn
Tae-Jin Lee
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 CN201480069142.1A priority Critical patent/CN105829279B/en
Priority to JP2016538774A priority patent/JP6535671B2/en
Publication of WO2015099485A1 publication Critical patent/WO2015099485A1/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 device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • 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 [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in an organic EL device is the light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched.
  • 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 materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • an organic EL device has a structure of a multilayer comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.
  • the selection of a compound comprised in the hole transport layer is known as a method for improving the characteristics of a device such as hole transport efficiency to the light-emitting layer, luminous efficiency, lifespan, etc.
  • 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
  • MTDATA 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine
  • an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A
  • Japanese Patent Appln. Laying-Open No. JP 2001-196177 discloses a compound in which two benzene rings of a fluorene are each substituted with a diarylamine, as an organic electroluminescent compound.
  • the above reference does not disclose an organic electroluminescent device using a compound in which one benzene ring of a fluorene is substituted with two diarylamines.
  • the objective of the present invention is to provide an organic electroluminescent compound having excellent luminous efficiency and lifespan characteristics.
  • 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;
  • Ar 1 to Ar 4 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
  • R 1 and R 2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
  • R 3 represents hydrogen, deuterium, a halogen, 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 (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR 4 R 5 , -SiR 6 R 7 R 8 , a cyano, a nitro, or a hydroxyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
  • R 4 and R 5 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
  • R 6 to R 8 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 (3- to 30-membered)heteroaryl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
  • a represents an integer of 1 to 4, where a is an integer of 2 or more, each of R 3 may be the same or different;
  • organic electroluminescent compound according to the present invention By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device having excellent current and luminous efficiencies.
  • the present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
  • the organic electroluminescent compound represented by the above formula 1 will be described in detail.
  • (C1-C30)alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, 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 meant to be a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably
  • the compound of formula 1 can be represented by the following formula 2:
  • L 1 , L 2 , Ar 1 to Ar 4 , R 1 to R 3 , and a are as defined in formula 1.
  • 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 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, preferably each independently represent a single bond, a substituted or unsubstituted (C6-C12)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene, and more preferably each independently represent a single bond, an unsubstituted (C6-C12)arylene, or an unsubstituted (5- to 20-membered)heteroarylene.
  • Ar 1 to Ar 4 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl, preferably each independently represent a substituted or unsubstituted (C6-C15)aryl, and more preferably each independently represent a (C6-C15)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a (5- to 20-membered)heteroaryl.
  • R 1 and R 2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring, preferably each independently represent a substituted or unsubstituted (C1-C6)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C
  • R 3 represents hydrogen, deuterium, a halogen, 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 (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR 4 R 5 , -SiR 6 R 7 R 8 , a cyano, a nitro, or a hydroxyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring, preferably each independently represent hydrogen, a substituted or
  • R 4 and R 5 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl, preferably each independently represent a substituted or unsubstituted (C6-C12)aryl, and more preferably each independently represent an unsubstituted (C6-C12)aryl.
  • R 6 to R 8 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 (3- to 30-membered)heteroaryl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur, preferably each independently represent a substituted or unsubstituted (C1-C6)alkyl, and more preferably each independently represent an unsubstituted (C1-C6)alky
  • a represents an integer of 1 to 4, preferably represents an integer of 1 to 2; and where a is an integer of 2 or more, each of R 3 may be the same or different.
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted (C6-C12)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene;
  • Ar 1 to Ar 4 each independently represent a substituted or unsubstituted (C6-C15)aryl;
  • R 1 and R 2 each independently represent a substituted or unsubstituted (C1-C6)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C6-C20) alicyclic or aromatic ring;
  • R 3 represents hydrogen, a substituted or unsubstituted (C6-C12)aryl, a substituted or unsubstituted (C5-C
  • L 1 and L 2 each independently represent a single bond, an unsubstituted (C6-C12)arylene, or an unsubstituted (5- to 20-membered)heteroarylene;
  • Ar 1 to Ar 4 each independently represent a (C6-C15)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a (5- to 20-membered)heteroaryl;
  • R 1 and R 2 each independently represent an unsubstituted (C1-C6)alkyl; a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C25)aryl, or a (5- to 20-membered)heteroaryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a
  • the specific compounds of the present invention include the following compounds, but are not limited thereto:
  • organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction scheme.
  • L 1 , L 2 , Ar 1 to Ar 4 , R 1 to R 3 , and a are as defined in formula 1 above.
  • 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 above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes.
  • the organic layer may comprise at least one organic electroluminescent compound of formula 1.
  • the organic layer comprises 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, a hole blocking layer, and an electron blocking layer.
  • the organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound of the present invention can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound of the present invention can be comprised as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more compounds other than the organic electroluminescent compound according to the present invention as host materials, and can further comprise one or more dopants.
  • the organic electroluminescent compound according to the present invention is comprised as a host material (first host material)
  • the other compound may be comprised as a second host material.
  • the weight ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
  • the host material other than the organic electroluminescent compound according to the present invention can be from any of the known phosphorescent hosts. Specifically, the phosphorescent host selected from the group consisting of the compounds of formulae 11 to 13 below is preferable in terms of luminous efficiency.
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -SiR 25 R 26 R 27 ;
  • 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 or unsubstituted (5- to 30-membered)heteroaryl;
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )-, or -C(R 32 )(R 33 )-, provided that Y 1 and Y 2 do not simultaneously exist;
  • R 31 to R 33 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, 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, b, and c each independently represent an integer of 0 to 4.
  • each of (Cz-L 4 ), each of (Cz), each of R 21 , each of R 22 , each of R 23 , or each of R 24 may be the same or different.
  • preferable examples of the host material are as follows:
  • the dopant comprised in the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant.
  • the dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopants may be preferably selected from compounds represented by the following formulae 101 to 103.
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 , and R 111 to R 123 each independently represent hydrogen; deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen(s); a cyano; a substituted or unsubstituted (C1-C30)alkoxy; a substituted or unsubstituted (C6-C30)aryl; or a substituted or unsubstituted (C3-C30)cycloalkyl; R 106 to R 109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g.
  • R 120 to R 123 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. quinoline unsubstituted or substituted with a halogen, alkyl, or aryl;
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and R 124 to R 127 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl, and R 208 to R 211 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
  • f and g each independently represent an integer of 1 to 3; where f or g is an integer of 2 or more, each of R 100 may be the same or different; and
  • n an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • compositions for preparing an organic electroluminescent device comprises the compound according to the present invention as a host material or a hole transport material.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes.
  • the organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for preparing the organic electroluminescent device according to the present invention.
  • the organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by 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 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 said metal.
  • the organic layer may further comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device according to 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 according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
  • a surface layer is preferably 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.
  • said chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and said metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably 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; 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 electroluminescent layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • An OLED device was produced using the organic electroluminescent compound according to the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone and isopropan alcohol, sequentially, and then was stored in isopropan alcohol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 4 ,N 4' -biphenyl-N 4 ,N 4' -bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-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 first hole injection layer having a thickness of 80 nm on the ITO substrate.
  • 1,4,5,8,9,11-hexaazatriphenylenhexacarbonitrile was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer.
  • compound T-1 as below was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer.
  • compound C-1 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer.
  • compound H-1 was introduced into one cell of the vacuum vapor depositing apparatus, as a host, and compound D-96 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates and were deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer.
  • the produced OLED device showed a red emission having a luminance of 800 cd/m 2 and a current density of 2.8 mA/cm 2 .
  • the time period for the luminance to decrease to 90% at 5,000 nits was 800 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-9 to form the second hole transport layer in a thickness of 60 nm.
  • the produced OLED device showed a red emission having a luminance of 1500 cd/m 2 and a current density of 5.2 mA/cm 2 .
  • the time period for the luminance to decrease to 90% at 5,000 nits was 750 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-67 to form the second hole transport layer in a thickness of 60 nm.
  • the produced OLED device showed a red emission having a luminance of 1200 cd/m 2 and a current density of 4.2 mA/cm 2 .
  • the time period for the luminance to decrease to 90% at 5,000 nits was 780 hours.
  • Comparative Example 1 Production of an OLED device comprising a
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating the compound below to form the second hole transport layer in a thickness of 60 nm.
  • the produced OLED device showed a red emission having a luminance of 2000 cd/m 2 and a current density of 11.2 mA/cm 2 .
  • the time period for the luminance to decrease to 90% at 5,000 nits was 67 hours.
  • an organic electroluminescent device using the organic electroluminescent compound according to the present invention has excellent luminous and lifespan characteristics.

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. By using the organic electroluminescent compound according to the present invention, it is possible to produce an organic electroluminescent device having excellent current efficiency and lifespan characteristics.

Description

AN ORGANIC ELECTROLUMINESCENT COMPOUND AND AN 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 device (EL device) is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. 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 [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in an organic EL device is the light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched. 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 materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known phosphorescent host materials. Recently, Pioneer (Japan) et al. developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc. as host materials, which were known as hole blocking layer materials.
Though these 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, and the lifespan of the device decreases. (2) The power efficiency of an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although an 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) Further, the operational lifespan of an organic EL device is short and luminous efficiency is still required to be improved.
Meanwhile, in order to enhance its efficiency and stability, an organic EL device has a structure of a multilayer comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. The selection of a compound comprised in the hole transport layer is known as a method for improving the characteristics of a device such as hole transport efficiency to the light-emitting layer, luminous efficiency, lifespan, etc.
In this regard, 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. were used as a hole injection and transport material. However, an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
Therefore, a hole transport layer for improving durability of an organic EL device still needs to be developed.
Japanese Patent Appln. Laying-Open No. JP 2001-196177 discloses a compound in which two benzene rings of a fluorene are each substituted with a diarylamine, as an organic electroluminescent compound. However, the above reference does not disclose an organic electroluminescent device using a compound in which one benzene ring of a fluorene is substituted with two diarylamines.
The objective of the present invention is to provide an organic electroluminescent compound having excellent luminous efficiency and lifespan characteristics.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2014012893-appb-I000001
wherein
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;
Ar1 to Ar4 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
R1 and R2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
R3 represents hydrogen, deuterium, a halogen, 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 (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR4R5, -SiR6R7R8, a cyano, a nitro, or a hydroxyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
R4 and R5 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
R6 to R8 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 (3- to 30-membered)heteroaryl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
a represents an integer of 1 to 4, where a is an integer of 2 or more, each of R3 may be the same or different; and
the heteroaryl(ene) and the heterocycloalkyl 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 according to the present invention, it is possible to manufacture an organic electroluminescent device having excellent current and luminous efficiencies.
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 of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
The organic electroluminescent compound represented by the above formula 1 will be described in detail.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, 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 meant to be 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 3 to 7 ring backbone atoms, including at least one heteroatom selected from B, N, O, S, P(=O), Si, and P, preferably O, S, and N, 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, 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)” is an aryl having 3 to 30 ring backbone atoms, including at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si, and P; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Further, “halogen” includes F, Cl, Br and I.
According to an embodiment of the present invention, the compound of formula 1 can be represented by the following formula 2:
wherein L1, L2, Ar1 to Ar4, R1 to R3, and a are as defined in formula 1.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. The substituents of the substituted (C1-C30)alkyl, the substituted (C3-C30)cycloalkyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (3- to 30-membered)heteroaryl(ene), and the substituted (C6-C30)aryl(C1-C30)alkyl in L1, L2, Ar1 to Ar4, and R1 to R8 of formula 1 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7-membered)heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (3- to 30-membered)heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di- (C1-C30)alkylamino, a mono- or di- (C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl, and preferably each independently are at least one selected from the group consisting of a (C1-C6)alkyl, a (C6-C25)aryl, and a (5- to 20-membered)heteroaryl.
In formula 1 above, 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, preferably each independently represent a single bond, a substituted or unsubstituted (C6-C12)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene, and more preferably each independently represent a single bond, an unsubstituted (C6-C12)arylene, or an unsubstituted (5- to 20-membered)heteroarylene.
Ar1 to Ar4 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl, preferably each independently represent a substituted or unsubstituted (C6-C15)aryl, and more preferably each independently represent a (C6-C15)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a (5- to 20-membered)heteroaryl.
R1 and R2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring, preferably each independently represent a substituted or unsubstituted (C1-C6)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C6-C20) alicyclic or aromatic ring, and more preferably each independently represent an unsubstituted (C1-C6)alkyl; a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C25)aryl, or a (5- to 20-membered)heteroaryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or are linked to each other to form a mono- or polycyclic (C6-C20) aromatic ring.
R3 represents hydrogen, deuterium, a halogen, 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 (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR4R5, -SiR6R7R8, a cyano, a nitro, or a hydroxyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring, preferably each independently represent hydrogen, a substituted or unsubstituted (C6-C12)aryl, a substituted or unsubstituted (C5-C12)cycloalkyl, -NR4R5, or -SiR6R7R8; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C6-C12) alicyclic or aromatic ring, and more preferably each independently represent hydrogen, an unsubstituted (C6-C12)aryl, an unsubstituted (C5-C12)cycloalkyl, -NR4R5, or -SiR6R7R8; or are linked to an adjacent substituent(s) to form a monocyclic (C6-C12) aromatic ring.
R4 and R5 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl, preferably each independently represent a substituted or unsubstituted (C6-C12)aryl, and more preferably each independently represent an unsubstituted (C6-C12)aryl.
R6 to R8 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 (3- to 30-membered)heteroaryl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur, preferably each independently represent a substituted or unsubstituted (C1-C6)alkyl, and more preferably each independently represent an unsubstituted (C1-C6)alkyl.
a represents an integer of 1 to 4, preferably represents an integer of 1 to 2; and where a is an integer of 2 or more, each of R3 may be the same or different.
The heteroaryl(ene) and the heterocycloalkyl each independently contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P.
According to one embodiment of the present invention, in formula 1 above, L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C12)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene; Ar1 to Ar4 each independently represent a substituted or unsubstituted (C6-C15)aryl; R1 and R2 each independently represent a substituted or unsubstituted (C1-C6)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C6-C20) alicyclic or aromatic ring; R3 represents hydrogen, a substituted or unsubstituted (C6-C12)aryl, a substituted or unsubstituted (C5-C12)cycloalkyl, -NR4R5, or -SiR6R7R8; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C6-C12) alicyclic or aromatic ring; R4 and R5 each independently represent a substituted or unsubstituted (C6-C12)aryl; R6 to R8 each independently represent a substituted or unsubstituted (C1-C6)alkyl; and a represents an integer of 1 to 2.
According to another embodiment of the present invention, in formula 1 above, L1 and L2 each independently represent a single bond, an unsubstituted (C6-C12)arylene, or an unsubstituted (5- to 20-membered)heteroarylene; Ar1 to Ar4 each independently represent a (C6-C15)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a (5- to 20-membered)heteroaryl; R1 and R2 each independently represent an unsubstituted (C1-C6)alkyl; a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C25)aryl, or a (5- to 20-membered)heteroaryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or are linked to each other to form a mono- or polycyclic (C6-C20) aromatic ring; R3 represents hydrogen, an unsubstituted (C6-C12)aryl, an unsubstituted (C5-C12)cycloalkyl, -NR4R5, or -SiR6R7R8; or are linked to an adjacent substituent(s) to form a monocyclic (C6-C12) aromatic ring; R4 and R5 each independently represent an unsubstituted (C6-C12)aryl; R6 to R8 each independently represent an unsubstituted (C1-C6)alkyl; and a represents an integer of 1 to 2.
The specific compounds of the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2014012893-appb-I000003
Figure PCTKR2014012893-appb-I000004
Figure PCTKR2014012893-appb-I000005
Figure PCTKR2014012893-appb-I000006
Figure PCTKR2014012893-appb-I000007
Figure PCTKR2014012893-appb-I000008
Figure PCTKR2014012893-appb-I000009
Figure PCTKR2014012893-appb-I000010
Figure PCTKR2014012893-appb-I000011
Figure PCTKR2014012893-appb-I000012
Figure PCTKR2014012893-appb-I000013
Figure PCTKR2014012893-appb-I000014
Figure PCTKR2014012893-appb-I000015
Figure PCTKR2014012893-appb-I000016
Figure PCTKR2014012893-appb-I000017
Figure PCTKR2014012893-appb-I000018
The organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction scheme.
[Reaction Scheme 1]
Figure PCTKR2014012893-appb-I000019
wherein L1, L2, Ar1 to Ar4, R1 to R3, and a are as defined in formula 1 above.
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 above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
The organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes. The organic layer may comprise at least one organic electroluminescent compound of formula 1.
One of the first and second electrodes can be an anode, and the other can be a cathode. The organic layer comprises 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, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound of the present invention can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound of the present invention can be comprised as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more compounds other than the organic electroluminescent compound according to the present invention as host materials, and can further comprise one or more dopants.
Where the organic electroluminescent compound according to the present invention is comprised as a host material (first host material), the other compound may be comprised as a second host material. Herein, the weight ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
The host material other than the organic electroluminescent compound according to the present invention can be from any of the known phosphorescent hosts. Specifically, the phosphorescent host selected from the group consisting of the compounds of formulae 11 to 13 below is preferable in terms of luminous efficiency.
Figure PCTKR2014012893-appb-I000020
Figure PCTKR2014012893-appb-I000021
Figure PCTKR2014012893-appb-I000022
wherein Cz represents the following structure;
Figure PCTKR2014012893-appb-I000023
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -SiR25R26R27;
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, and R32 and R33 may be the same or different;
h and i each independently represent an integer of 1 to 3;
j, k, b, and c each independently represent an integer of 0 to 4; and
where h, i, j, k, b, or c is an integer of 2 or more, each of (Cz-L4), each of (Cz), each of R21, each of R22, each of R23, or each of R24 may be the same or different.
Specifically, preferable examples of the host material are as follows:
Figure PCTKR2014012893-appb-I000024
Figure PCTKR2014012893-appb-I000025
Figure PCTKR2014012893-appb-I000026
Figure PCTKR2014012893-appb-I000027
Figure PCTKR2014012893-appb-I000028
Figure PCTKR2014012893-appb-I000029
Figure PCTKR2014012893-appb-I000030
Figure PCTKR2014012893-appb-I000031
Figure PCTKR2014012893-appb-I000032
Figure PCTKR2014012893-appb-I000033
Figure PCTKR2014012893-appb-I000034
Figure PCTKR2014012893-appb-I000035
Figure PCTKR2014012893-appb-I000036
Figure PCTKR2014012893-appb-I000037
Figure PCTKR2014012893-appb-I000038
Figure PCTKR2014012893-appb-I000039
Figure PCTKR2014012893-appb-I000040
[wherein TPS represents triphenylsilyl]
The dopant comprised in the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant. The dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopants may be preferably selected from compounds represented by the following formulae 101 to 103.
Figure PCTKR2014012893-appb-I000041
Figure PCTKR2014012893-appb-I000042
Figure PCTKR2014012893-appb-I000043
wherein L is selected from the following structures:
Figure PCTKR2014012893-appb-I000044
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
R101 to R109, and R111 to R123 each independently represent hydrogen; deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen(s); a cyano; a substituted or unsubstituted (C1-C30)alkoxy; a substituted or unsubstituted (C6-C30)aryl; or a substituted or unsubstituted (C3-C30)cycloalkyl; R106 to R109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl; and R120 to R123 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. quinoline unsubstituted or substituted with a halogen, alkyl, or aryl;
R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and R124 to R127 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl, and R208 to R211 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
f and g each independently represent an integer of 1 to 3; where f or g 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 phosphorescent dopant materials include the following:
Figure PCTKR2014012893-appb-I000045
Figure PCTKR2014012893-appb-I000046
Figure PCTKR2014012893-appb-I000047
Figure PCTKR2014012893-appb-I000048
Figure PCTKR2014012893-appb-I000050
Figure PCTKR2014012893-appb-I000051
Figure PCTKR2014012893-appb-I000052
Figure PCTKR2014012893-appb-I000053
Figure PCTKR2014012893-appb-I000054
Figure PCTKR2014012893-appb-I000055
Figure PCTKR2014012893-appb-I000056
Figure PCTKR2014012893-appb-I000057
Figure PCTKR2014012893-appb-I000058
Figure PCTKR2014012893-appb-I000059
Figure PCTKR2014012893-appb-I000060
Figure PCTKR2014012893-appb-I000061
Figure PCTKR2014012893-appb-I000062
Figure PCTKR2014012893-appb-I000063
Figure PCTKR2014012893-appb-I000064
Figure PCTKR2014012893-appb-I000065
Figure PCTKR2014012893-appb-I000066
Figure PCTKR2014012893-appb-I000067
Figure PCTKR2014012893-appb-I000068
Figure PCTKR2014012893-appb-I000069
Figure PCTKR2014012893-appb-I000070
In another embodiment of the present invention, a composition for preparing an organic electroluminescent device is provided. The composition comprises the compound according to the present invention as a host material or a hole transport material.
In addition, the organic electroluminescent device according to the present invention comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes. The organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for preparing the organic electroluminescent device according to the present invention.
The organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device according to the present invention, the organic layer may further comprise 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 said metal. The organic layer may further comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device according to 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 according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
According to the present invention, at least one layer (hereinafter, "a surface layer”) is preferably 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, said chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and said metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device according to the present invention, a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably 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. 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 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 electroluminescent layers and emitting white light.
In order to form each layer of the organic electroluminescent device according to 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 organic electroluminescent compound, 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 C-1
Figure PCTKR2014012893-appb-I000071
Preparation of compound 1-2
After introducing 2,4-dichlorophenyl boronic acid (compound 1-1) (64 g, 335 mmol), methyl 2-bromobenzoate (60 g, 279 mmol), tetrakis(triphenylphosphine)palladium (9.5 g, 8.4 mmol), potassium carbonate (96 g, 698 mmol), toluene 600 mL, and ethanol 300 mL in a reaction container, distilled water 300 mL was added to the mixture, and the mixture was stirred at 120°C for 3 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 1-2 (79 g, 99%).
Preparation of compound 1-3
After introducing compound 1-2 (79 g, 279 mmol), Eaton’s reagent 110 mL, and chlorobenzene 1 L in a reaction container, the mixture was stirred under reflux overnight. After cooling the reaction solution to room temperature, the reaction was completed with water, and an organic layer was extracted with methylene chloride. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 1-3 (49 g, 71%).
Preparation of compound 1-4
After introducing iodine (18 g, 71 mmol), hypophosphorous acid (35 mL, 315 mmol, 50% aqueous solution), and acetic acid 1 L in a reaction container, the mixture was stirred at 100°C for 30 minutes. Thereafter, compound 1-3 was slowly added dropwise thereto, and the mixture was stirred under reflux overnight. After cooling the reaction solution to room temperature, the precipitated solid was filtered, and washed with a large amount of hexane. The filtrate was diluted with ethylacetate and washed with water. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 1-4 (35.7 g, 77%).
Preparation of compound 1-5
After introducing compound 1-4 (35.5 g, 151 mmol), potassium hydroxide (42 g, 760 mmol), potassium iodide (2.5 g, 15 mmol), benzyltriethylammonium chloride (1.7 g, 7.8 mmol), distilled water 700 mL, and dimethyl sulfoxide 700 mL in a reaction container, the mixture was stirred at room temperature for 15 minutes. Thereafter, methyl iodide (25 mL, 378 mmol) was added thereto, and the mixture was stirred at room temperature overnight. The reaction solution was diluted with ethylacetate and washed with distilled water. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 1-5 (32 g, 81%).
Preparation of compound C-1
After introducing compound 1-5 (7 g, 26.6 mmol), dibiphenyl-4-ylamine (17 g, 52.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.9 g, 2.1 mmol), s-phos (1.1 g, 2.7 mmol), sodium t-butoxide (6.4 g, 67 mmol), and o-xylene 150 mL in a reaction container, the mixture was stirred under reflux for 1 hour. Thereafter, the reaction solution cooled to room temperature was diluted with ethylacetate and washed with water several times. The extracted organic layer was then dried with anhydrous magnesium sulfate, distilled under reduced pressure, and purified with column chromatography to obtain compound C-1 (9.6 g, 55%).
Example 2: Preparation of compound C-9
Figure PCTKR2014012893-appb-I000072
Preparation of compound 2-1
After introducing compound 3-1 (20.5 g, 82.3 mol) and tetrahydrofuran 400 mL in a reaction container, the reaction solution was cooled to 0°C, and phenylmagnesium bromide (40 mL, 123 mmol) and 3 M diethylether solution were slowly added dropwise thereto. The reaction solution was stirred at room temperature for 1 hour. Thereafter, the reaction was completed with ammonium chloride aqueous solution, and the reaction solution was diluted with ethylacetate and washed with water. The extracted organic layer was then dried with anhydrous magnesium sulfate, distilled under reduced pressure, and purified with column chromatography to obtain compound 2-1 (28 g, 99%).
Preparation of compound 2-2
After introducing compound 2-1 (15.8 g, 48.3 mmol), 9-phenylcarbazole (17.6 g, 72.5 mmol), and methylenechloride (MC) 250 mL in a reaction container, the mixture was subjected into nitrogen atmosphere. Eaton’s reagent 1.5 mL was then slowly added dropwise thereto, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction was completed with distilled water, and the mixture was extracted with methylenechloride. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-2 (13.2 g, 49%).
Preparation of compound C-9
After introducing compound 2-2 (13 g, 26.6 mmol), dibiphenylamine (8 g, 47 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.7 g, 1.9 mmol), s-phos (0.96 g, 2.35 mmol), sodium t-butoxide (5.6 g, 58.8 mmol), and o-xylene 120 mL in a reaction container, the mixture was stirred under reflux overnight. Thereafter, the reaction solution cooled to room temperature was diluted with ethylacetate and washed with water several times. The extracted organic layer was then dried with anhydrous magnesium sulfate, distilled under reduced pressure, and purified with column chromatography to obtain compound C-9 (10 g, 52%).
Device Example 1: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced using the organic electroluminescent compound according to the present invention. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone and isopropan alcohol, sequentially, and then was stored in isopropan alcohol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N4,N4'-biphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-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 first hole injection layer having a thickness of 80 nm on the ITO substrate. Then, 1,4,5,8,9,11-hexaazatriphenylenhexacarbonitrile (HAT-CN) was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer. Then, compound T-1 as below was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer. Then, compound C-1 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer. Thereafter, compound H-1 was introduced into one cell of the vacuum vapor depositing apparatus, as a host, and compound D-96 was introduced into another cell as a dopant. The two materials were evaporated at different rates and were deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer. Then, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 35 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 80 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 a red emission having a luminance of 800 cd/m2 and a current density of 2.8 mA/cm2. As for the lifespan characteristic, the time period for the luminance to decrease to 90% at 5,000 nits was 800 hours.
Figure PCTKR2014012893-appb-I000073
Device Example 2: Production of an OLED device 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 for evaporating compound C-9 to form the second hole transport layer in a thickness of 60 nm.
The produced OLED device showed a red emission having a luminance of 1500 cd/m2 and a current density of 5.2 mA/cm2. As for the lifespan characteristic, the time period for the luminance to decrease to 90% at 5,000 nits was 750 hours.
Device Example 3: Production of an OLED device 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 for evaporating compound C-67 to form the second hole transport layer in a thickness of 60 nm.
The produced OLED device showed a red emission having a luminance of 1200 cd/m2 and a current density of 4.2 mA/cm2. As for the lifespan characteristic, the time period for the luminance to decrease to 90% at 5,000 nits was 780 hours.
Comparative Example 1: Production of an OLED device comprising a
conventional organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 1, except for evaporating the compound below to form the second hole transport layer in a thickness of 60 nm.
The produced OLED device showed a red emission having a luminance of 2000 cd/m2 and a current density of 11.2 mA/cm2. As for the lifespan characteristic, the time period for the luminance to decrease to 90% at 5,000 nits was 67 hours.
Figure PCTKR2014012893-appb-I000074
It is verified that the luminous characteristics of the organic electroluminescent compound according to the present invention is superior to the conventional materials. In addition, an organic electroluminescent device using the organic electroluminescent compound according to the present invention has excellent luminous and lifespan characteristics.

Claims (7)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014012893-appb-I000075
    wherein
    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;
    Ar1 to Ar4 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    R1 and R2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
    R3 represents hydrogen, deuterium, a halogen, 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 (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR4R5, -SiR6R7R8, a cyano, a nitro, or a hydroxyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
    R4 and R5 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    R6 to R8 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 (3- to 30-membered)heteroaryl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
    a represents an integer of 1 to 4, where a is an integer of 2 or more, each of R3 may be the same or different; and
    the heteroaryl(ene) and the heterocycloalkyl 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 is represented by the following formula 2:
    Figure PCTKR2014012893-appb-I000076
    wherein L1, L2, Ar1 to Ar4, R1 to R3, and a are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl, the substituted (C3-C30)cycloalkyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (3- to 30-membered)heteroaryl(ene), and the substituted (C6-C30)aryl(C1-C30)alkyl in L1, L2, Ar1 to Ar4, and R1 to R8 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7-membered)heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (3- to 30-membered)heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di- (C1-C30)alkylamino, a mono- or di- (C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl.
  4. The organic electroluminescent compound according to claim 1, wherein
    L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C12)arylene, or a substituted or unsubstituted (5- to 20-membered)heteroarylene;
    Ar1 to Ar4 each independently represent a substituted or unsubstituted (C6-C15)aryl;
    R1 and R2 each independently represent a substituted or unsubstituted (C1-C6)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or are linked to each other to form a mono- or polycyclic (C6-C20) alicyclic or aromatic ring;
    R3 represents hydrogen, a substituted or unsubstituted (C6-C12)aryl, a substituted or unsubstituted (C5-C12)cycloalkyl, -NR4R5, or -SiR6R7R8; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C6-C12) alicyclic or aromatic ring;
    R4 and R5 each independently represent a substituted or unsubstituted (C6-C12)aryl;
    R6 to R8 each independently represent a substituted or unsubstituted (C1-C6)alkyl; and
    a represents an integer of 1 to 2.
  5. The organic electroluminescent compound according to claim 1, wherein
    L1 and L2 each independently represent a single bond, an unsubstituted (C6-C12)arylene, or an unsubstituted (5- to 20-membered)heteroarylene;
    Ar1 to Ar4 each independently represent a (C6-C15)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a (5- to 20-membered)heteroaryl;
    R1 and R2 each independently represent an unsubstituted (C1-C6)alkyl; a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C25)aryl, or a (5- to 20-membered)heteroaryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or are linked to each other to form a mono- or polycyclic (C6-C20) aromatic ring;
    R3 represents hydrogen, an unsubstituted (C6-C12)aryl, an unsubstituted (C5-C12)cycloalkyl, -NR4R5, or -SiR6R7R8; or are linked to an adjacent substituent(s) to form a monocyclic (C6-C12) aromatic ring;
    R4 and R5 each independently represent an unsubstituted (C6-C12)aryl;
    R6 to R8 each independently represent an unsubstituted (C1-C6)alkyl; and
    a represents an integer of 1 to 2.
  6. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2014012893-appb-I000077
    Figure PCTKR2014012893-appb-I000078
    Figure PCTKR2014012893-appb-I000079
    Figure PCTKR2014012893-appb-I000080
    Figure PCTKR2014012893-appb-I000081
    Figure PCTKR2014012893-appb-I000082
    Figure PCTKR2014012893-appb-I000083
    Figure PCTKR2014012893-appb-I000084
    Figure PCTKR2014012893-appb-I000085
    Figure PCTKR2014012893-appb-I000086
    Figure PCTKR2014012893-appb-I000087
    Figure PCTKR2014012893-appb-I000088
    Figure PCTKR2014012893-appb-I000089
    Figure PCTKR2014012893-appb-I000090
    Figure PCTKR2014012893-appb-I000091
    Figure PCTKR2014012893-appb-I000092
  7. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
PCT/KR2014/012893 2013-12-26 2014-12-26 An organic electroluminescent compound and an organic electroluminescent device comprising the same WO2015099485A1 (en)

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