WO2015012618A1 - Organic electroluminescent compound and organic electroluminescent device comprising the same - Google Patents

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

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WO2015012618A1
WO2015012618A1 PCT/KR2014/006754 KR2014006754W WO2015012618A1 WO 2015012618 A1 WO2015012618 A1 WO 2015012618A1 KR 2014006754 W KR2014006754 W KR 2014006754W WO 2015012618 A1 WO2015012618 A1 WO 2015012618A1
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substituted
unsubstituted
aryl
alkyl
membered
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PCT/KR2014/006754
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French (fr)
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Soo-Jin Yang
Doo-Hyeon Moon
Ji-Song JUN
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 CN201480038815.7A priority Critical patent/CN105358654B/en
Publication of WO2015012618A1 publication Critical patent/WO2015012618A1/en

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Definitions

  • the present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
  • An electroluminescent (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 to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • 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 material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials have been widely being researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C-3’)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.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • the organic EL device may be manufactured with a multi-layered structure in which a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc., are comprised.
  • a compound for the hole transport layer is important to enhance characteristics of the device, such as efficiency for transporting holes to the light-emitting layer, luminous efficiency, and lifespan.
  • 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
  • WO 2012/034627 discloses compounds for an organic EL device, in which only one substituent selected from a diarylamine, a heteroarylamine, and a nitrogen-containing heteroaryl group is bonded, directly or via a linker such as aryl, to a benzene ring of spirofluorene.
  • this reference fails to specifically disclose a compound in which two substituents are bonded to a linker or a benzene ring of spirofluorene, and an organic electroluminescent device employing the same for a hole transport layer.
  • the objective of the present disclosure is to provide an organic electroluminescent compound showing excellence in current efficiency and thermal stability due to high glass transition temperature.
  • the organic electroluminescent compound represented by formula 1, of the present disclosure includes a spirofluorene structure as a mother nucleus, which provides high glass transition temperature and excellent thermal stability.
  • Ar 1 to Ar 4 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, 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;
  • Ar 5 to Ar 8 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (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;
  • n and n each independently, represent an integer of 0 to 2; where m or n is 2, each of -N(Ar 1 )(Ar 2 ) or each of -N(Ar 3 )(Ar 4 ) may be the same or different;
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; where m is 0, L 1 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
  • L 2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; where n is 0, L 2 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
  • o 1 or 2; where o is 2, each of Ar 5 may be the same or different;
  • p, q, and r each independently, represent an integer of 1 to 4; where p, q, or r is an integer of 2 or more, each of Ar 6 , each of Ar 7 , or each of Ar 8 may be the same or different;
  • R 1 to R 3 each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or R 1 and R 2 may be linked to each other to
  • the compound of formula 1 may be preferably represented by the following formula 2 or 3.
  • Ar 1 to Ar 4 each independently, represent a substituted or unsubstituted (C6-C30)aryl
  • L 1 , L 2 , Ar 5 to Ar 8 , and o to r are as defined in formula 1.
  • the compound of formula 1 may be preferably represented by the following formula 4.
  • Ar 1 and Ar 2 each independently, represent a substituted or unsubstituted (C6-C30)aryl
  • L 1 ' represents a substituted or unsubstituted (C6-C30)arylene
  • Ar 5 to Ar 8 , and o to r are as defined in formula 1.
  • the organic electroluminescent compound of the present disclosure can provide an organic electroluminescent device showing excellence in current efficienty and thermal stability due to its high glass transition temperature (Tg).
  • the present disclosure provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
  • (C1-C30)alkyl indicates a linear or branched alkyl having 1 to 30, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • “(C3-C30)cycloalkyl” indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferably 3 to 20, and more preferably 3 to 7 carbon atoms and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • (C6-C30)aryl(ene) indicates a monocyclic or fused ring derived from an aromatic hydrocarbon and having 6 to 30, preferably 6 to 20, and more preferably 6 to 15 ring backbone carbon atoms, 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.
  • substituents of the substituted alkyl, the substituted alkenyl, the substituted alkynyl, the substituted cycloalkyl, the substituted cycloalkenyl, the substituted heterocycloalkyl, the substituted aryl(ene) and the substituted heteroaryl(ene) in Ar 1 to Ar 8 , R 1 to R 3 , L 1 , and L 2 , 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
  • Ar 1 to Ar 4 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, 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; preferably, represent a substituted or unsubstituted (C6-C20)aryl; and more preferably, represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a di(C1-C6)alkyl(C6-C15)aryl.
  • Ar 1 to Ar 4 each independently, may be phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, phenanthrenyl, triphenylenyl, or fluoranthenyl.
  • Ar 1 and Ar 2 may be the same as Ar 3 or Ar 4 , wherein Ar 3 and Ar 4 may be the same or different.
  • Ar 5 to Ar 8 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (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; preferably represent hydrogen, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3- to 20-membered), mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and more preferably represent hydrogen, or may be linked to an adjacent substituent(
  • Ar 5 may be hydrogen; and one of Ar 6 to Ar 8 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted benzothiophene ring, or a substituted or unsubstituted indole ring.
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; preferably represents a single bond, or an unsubstituted (C6-C20)arylene; more preferably represents a single bond, or an unsubstituted (C6-C15)arylene; and specifically represents phenylene, biphenylene, or naphthylene.
  • L 1 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; and specifically represents hydrogen.
  • L 2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; preferably represents a single bond, or an unsubstituted (C6-C20)arylene; more preferably represents a single bond, or an unsubstituted (C6-C15)arylene; and specifically represents phenylene, biphenylene, or naphthylene.
  • L 2 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; and specifically represents hydrogen.
  • Ar 1 to Ar 4 each independently, represent a substituted or unsubstituted (C6-C20)aryl
  • Ar 5 to Ar 8 each independently, represet hydrogen, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3- to 20-membered), mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur
  • m is 1 or 2
  • L 1 represents a single bond or an unsubstituted (C6-C20)arylene
  • where m represents hydrogen
  • n is 1 or 2
  • L 2 represents a single bond or an unsubstituted (C6-C20)arylene
  • n 0, L 2 represents hydrogen
  • Ar 1 to Ar 4 each independently, represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a di(C1-C6)alkyl(C6-C15)aryl;
  • Ar 5 to Ar 8 each independently, represent hydrogen, or may be linked to an adjacent substituent(s) to form a (3- to 15-membered), mono- or polycyclic aromatic ring unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C15)aryl, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
  • m is 1 or 2
  • L 1 represents a single bond or an unsubstituted (C6-C15)arylene; where m is 0, L 1 represents hydrogen; where n is 1 or 2, L 2 represents a single bond
  • organic electroluminescent compound of formula 1 includes the following, but is not limited thereto:
  • the organic electroluminescent compound of the present disclosure can be prepared by a synthetic method known to one skilled in the art. For example, it can be prepared according to the following reaction scheme 1.
  • Ar 1 to Ar 8 , L 1 , L 2 , m, n, and o to r are as defined in formula 1 above, and Hal represents a halogen.
  • aryl amine and aryl halide are reacted with each other under a basic condition (e.g. by sodium t-butoxide) to form a carbon-nitrogen bond.
  • the reaction is carried out in an aromatic organic solvent such as toluene or xylene; and is usually performed under reflux by using palladium complex such as a combination of palladium acetate and S-Phos (2-dicyclophosphino-2’,6’-dimethoxyphenyl) as a catalyst.
  • the present disclosure 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 the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised for an organic electroluminescent device, in addition to the compound of the present disclosure.
  • 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, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the organic electroluminescent compound of the present disclosure may be comprised in at least one of the light-emitting layer and the hole transport layer.
  • the organic electroluminescent compound of the present disclosure may be comprised as a hole transport material.
  • the organic electroluminescent compound of the present disclosure may be comprised as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present disclosure may further comprise at least one compound other than the organic electroluminescent compound of the present disclosure, as a host material. Furthermore, the organic electroluminescent device may further comprise at least one dopant.
  • organic electroluminescent compound of the present disclosure is comprised as a host material (a first host material) in a light-emitting layer
  • another compound may be comprised as a second host material.
  • the weight ratio between the first host material and the second host material is in the range of 1:99 to 99:1.
  • the second host material may be from any of the known phosphorescent host materials. Specifically, the compound selected from the group consisting of the compounds of formulae 11 to 13 below is preferable as the second host material in view of luminous efficiency.
  • 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 (3- 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 or unsubstituted (5- to 30-membered
  • the second host material includes the following:
  • the dopant for the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopant may be preferably selected from the group consisting of compounds represented by the following formulae 101 to 103.
  • L is selected from the following structures:
  • R 100 represents hydrogen, or a substituted or unsubstituted (C1-C30)alkyl
  • 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 cyano, a substituted or unsubstituted (C1-C30)alkoxy, or a substituted or unsubstituted (C3-C30)cycloalkyl
  • R 120 to R 123 may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic 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 to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, e.g.
  • R 201 to R 211 each independently, represent hydrogen, deuterium, a halogen, or a (C1-C30)alkyl unsubstituted or substituted with a halogen;
  • c and d each independently, represent an integer of 1 to 3; where c or d is an integer of 2 or more, each of R 100 may be the same or different; and e represents an integer of 1 to 3.
  • the phosphorescent dopant material includes the following:
  • a mixture or composition for preparing an organic electroluminescent device comprises the compound of the present disclosure, as a host material or a hole transport material.
  • the mixture or composition may be a mixture or composition for preparing a light-emitting layer or a hole transport layer of an organic electroluminescent device.
  • the organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise a light-emitting layer, which may comprise the mixture or composition for the organic electroluminescent device of the present disclosure.
  • the organic electroluminescent device of the present disclosure may further comprise, in addition to the compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • the organic layer may further comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device of the present disclosure may emit white light by further comprising at least one light-emitting layer, which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound of the present disclosure. If necessary, it may further comprise 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 disclosure. 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.
  • 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.
  • OLED was produced using the compound of the present disclosure as follows.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) (Geomatec) was subjected to an ultrasonic washing with acetone and isopropanol, sequentially, and was then 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.
  • Compound C-2 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, 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole 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 1,100 cd/m 2 and a current density of 2.4 mA/cm 2 .
  • OLED was produced in the same manner as in Device Example 1, except that compound C-29 was used to form a hole transport layer having a thickness of 20 nm; and after introducing 7-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-7H-benzo[c]carbazole as a host material and compound D-87 as a dopant into the two cells of the vacuum vapor depositing apparatus, respectively, the two materials were evaporated at different rates, so that the dopant was 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 30 nm on the hole transport layer.
  • the produced OLED showed red emission having a luminance of 1,880 cd/m 2 and a current density of 13.2 mA/cm 2 .
  • OLED was produced in the same manner as in Device Example 1, except that compound C-8 was used to form a hole transport layer having a thickness of 20 nm.
  • the produced OLED showed green emission having a luminance of 1,400 cd/m 2 and a current density of 2.9 mA/cm 2 .
  • OLED was produced in the same manner as in Device Example 1, except that compound C-49 was used to form a hole transport layer having a thickness of 20 nm.
  • the produced OLED showed green emission having a luminance of 2,100 cd/m 2 and a current density of 4.4 mA/cm 2 .
  • OLED was produced in the same manner as in Device Example 2, except that compound C-40 was used to form a hole transport layer having a thickness of 20 nm.
  • the produced OLED showed red emission having a luminance of 2,500 cd/m 2 and a current density of 18.0 mA/cm 2 .
  • OLED was produced in the same manner as in Device Example 1, except that N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was used to form a hole transport layer having a thickness of 20 nm.
  • the produced OLED showed green emission having a luminance of 8,000 cd/m 2 and a current density of 20.9 mA/cm 2 .
  • OLED was produced in the same manner as in Device Example 2, except that N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was used to form a hole transport layer having a thickness of 20 nm.
  • the produced OLED showed red emission having a luminance of 6,000 cd/m 2 and a current density of 80.0 mA/cm 2 .
  • OLED was produced in the same manner as in Device Example 1, except that compound-1 was used to form a hole transport layer having a thickness of 20 nm.
  • the produced OLED showed green emission having a luminance of 9,000 cd/m 2 and a current density of 21.5 mA/cm 2 .
  • OLED was produced in the same manner as in Device Example 2, except that compound-1 was used to form a hole transport layer having a thickness of 20 nm.
  • the produced OLED showed red emission having a luminance of 7,000 cd/m 2 and a current density of 62.5 mA/cm 2 .
  • the organic electroluminescent compound of the present disclosure has high glass transition temperature, and provides higher current efficiency than conventional compounds.
  • the organic electroluminescent device shows excellent luminous efficiency, especially current efficienty by using the organic electroluminescent compound of the present disclosure.

Abstract

The present disclosure relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound of the present disclosure has high glass transition temperature, and thus shows good thermal stability. By using the organic electroluminescent compound of the present disclosure, an organic electroluminescent device showing excellent current efficiency can be provided.

Description

ORGANIC ELECTROLUMINESCENT COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
An electroluminescent (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 to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
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 material. 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 have been widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C-3’)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 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, which results in poor lifespan. (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.
To improve efficiencies and stability, the organic EL device may be manufactured with a multi-layered structure in which a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc., are comprised. In the structure, a compound for the hole transport layer is important to enhance characteristics of the device, such as efficiency for transporting holes to the light-emitting layer, luminous efficiency, and lifespan.
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 for an organic EL device. However, the organic EL device using these materials is problematic in quantum efficiency and lifespan. It is due to thermal stress occuring between an anode and a hole injection layer, when the organic EL device is driven under high current. Thermal stress significantly reduces the lifespan of the device. Furthermore, 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. The hole transport layer needs to be developed to enhance durability of the organic EL device.
WO 2012/034627 discloses compounds for an organic EL device, in which only one substituent selected from a diarylamine, a heteroarylamine, and a nitrogen-containing heteroaryl group is bonded, directly or via a linker such as aryl, to a benzene ring of spirofluorene. However, this reference fails to specifically disclose a compound in which two substituents are bonded to a linker or a benzene ring of spirofluorene, and an organic electroluminescent device employing the same for a hole transport layer.
The objective of the present disclosure is to provide an organic electroluminescent compound showing excellence in current efficiency and thermal stability due to high glass transition temperature.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1.
The organic electroluminescent compound represented by formula 1, of the present disclosure, includes a spirofluorene structure as a mother nucleus, which provides high glass transition temperature and excellent thermal stability.
Figure PCTKR2014006754-appb-I000001
wherein
Ar1 to Ar4, 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, 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;
Ar5 to Ar8, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (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;
m and n, each independently, represent an integer of 0 to 2; where m or n is 2, each of -N(Ar1)(Ar2) or each of -N(Ar3)(Ar4) may be the same or different;
m+n is 2;
where m is 1 or 2, L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; where m is 0, L1 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
where n is 1 or 2, L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; where n is 0, L2 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
o represents 1 or 2; where o is 2, each of Ar5 may be the same or different;
p, q, and r, each independently, represent an integer of 1 to 4; where p, q, or r is an integer of 2 or more, each of Ar6, each of Ar7, or each of Ar8 may be the same or different;
provided that ,
Figure PCTKR2014006754-appb-I000002
,
Figure PCTKR2014006754-appb-I000003
, and
Figure PCTKR2014006754-appb-I000004
(wherein X represents -O-, -S-, -C(R1)(R2)-, or -N(R3)-; R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or R1 and R2 may be linked to each other 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) are excluded; and
the heterocycloalkyl and heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P.
According to one aspect of the present disclosure, the compound of formula 1 may be preferably represented by the following formula 2 or 3.
Figure PCTKR2014006754-appb-I000005
Figure PCTKR2014006754-appb-I000006
wherein
Ar1 to Ar4, each independently, represent a substituted or unsubstituted (C6-C30)aryl;
m and n represent 1; and
L1, L2, Ar5 to Ar8, and o to r are as defined in formula 1.
According to another aspect of the present disclosure, the compound of formula 1 may be preferably represented by the following formula 4.
Figure PCTKR2014006754-appb-I000007
wherein
Ar1 and Ar2, each independently, represent a substituted or unsubstituted (C6-C30)aryl;
L1' represents a substituted or unsubstituted (C6-C30)arylene;
the two -N(Ar1)(Ar2) are bonded to L1' in meta position; and
Ar5 to Ar8, and o to r are as defined in formula 1.
The organic electroluminescent compounds in which two diarylamines are connected to the same aryl group in meta position as shown in formulae 2 to 4, have small band gap due to conjugation. Therefore, where they are used for a hole transport layer, the layer has relatively high triplet energy, and thus can block the transfer of excitons from a phosphorescent light-emitting layer to the hole transport layer.
The organic electroluminescent compound of the present disclosure can provide an organic electroluminescent device showing excellence in current efficienty and thermal stability due to its high glass transition temperature (Tg).
Hereinafter, the present disclosure 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 disclosure 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 details of the organic electroluminescent compound of formula 1 are as follows.
Herein, “(C1-C30)alkyl” indicates a linear or branched alkyl having 1 to 30, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “(C2-C30)alkynyl” indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. “(C3-C30)cycloalkyl” indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferably 3 to 20, and more preferably 3 to 7 carbon atoms and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “(3- to 7-membered) heterocycloalkyl” indicates a cycloalkyl having 3 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, “(C6-C30)aryl(ene)” indicates a monocyclic or fused ring derived from an aromatic hydrocarbon and having 6 to 30, preferably 6 to 20, and more preferably 6 to 15 ring backbone carbon atoms, 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. “(5- to 30-membered) heteroaryl(ene)” indicates an aryl group having 5 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, 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. In formula 1 of the present disclosure, the substituents of the substituted alkyl, the substituted alkenyl, the substituted alkynyl, the substituted cycloalkyl, the substituted cycloalkenyl, the substituted heterocycloalkyl, the substituted aryl(ene) and the substituted heteroaryl(ene) in Ar1 to Ar8, R1 to R3, L1, and L2, 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 (3- 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 unsubstituted or substituted with a (C1-C30)alkyl, 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 di(C1-C30)alkyl(C6-C30)aryl, a carboxy, a nitro, and a hydroxy; and preferably at least one selected from the group consisting of a (C1-C6)alkyl, a (C6-C15)aryl, and a di(C1-C6)alkyl(C6-C15)aryl.
Ar1 to Ar4, 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, 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; preferably, represent a substituted or unsubstituted (C6-C20)aryl; and more preferably, represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a di(C1-C6)alkyl(C6-C15)aryl. Specifically, Ar1 to Ar4, each independently, may be phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, phenanthrenyl, triphenylenyl, or fluoranthenyl. Preferably, in formula 2 or 3, at least one of Ar1 and Ar2 may be the same as Ar3 or Ar4, wherein Ar3 and Ar4 may be the same or different.
Ar5 to Ar8, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (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; preferably represent hydrogen, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3- to 20-membered), mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and more preferably represent hydrogen, or may be linked to an adjacent substituent(s) to form a (3- to 15-membered) mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur, and which may be unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C15)aryl. Specifically, Ar5 may be hydrogen; and one of Ar6 to Ar8 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted benzothiophene ring, or a substituted or unsubstituted indole ring.
Where m is 1 or 2, L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; preferably represents a single bond, or an unsubstituted (C6-C20)arylene; more preferably represents a single bond, or an unsubstituted (C6-C15)arylene; and specifically represents phenylene, biphenylene, or naphthylene. Where m is 0, L1 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; and specifically represents hydrogen.
Where n is 1 or 2, L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; preferably represents a single bond, or an unsubstituted (C6-C20)arylene; more preferably represents a single bond, or an unsubstituted (C6-C15)arylene; and specifically represents phenylene, biphenylene, or naphthylene. Where n is 0, L2 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; and specifically represents hydrogen.
According to one embodiment of the present disclosure, in formula 1, Ar1 to Ar4, each independently, represent a substituted or unsubstituted (C6-C20)aryl; Ar5 to Ar8, each independently, represet hydrogen, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3- to 20-membered), mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; where m is 1 or 2, L1 represents a single bond or an unsubstituted (C6-C20)arylene; where m is 0, L1 represents hydrogen; where n is 1 or 2, L2 represents a single bond or an unsubstituted (C6-C20)arylene; and where n is 0, L2 represents hydrogen.
According to another embodiment of the present disclosure, in formula 1, Ar1 to Ar4, each independently, represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a di(C1-C6)alkyl(C6-C15)aryl; Ar5 to Ar8, each independently, represent hydrogen, or may be linked to an adjacent substituent(s) to form a (3- to 15-membered), mono- or polycyclic aromatic ring unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C15)aryl, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; where m is 1 or 2, L1 represents a single bond or an unsubstituted (C6-C15)arylene; where m is 0, L1 represents hydrogen; where n is 1 or 2, L2 represents a single bond or an unsubstituted (C6-C15)arylene; and where n is 0, L2 represents hydrogen.
More specifically, the organic electroluminescent compound of formula 1 includes the following, but is not limited thereto:
Figure PCTKR2014006754-appb-I000008
Figure PCTKR2014006754-appb-I000009
Figure PCTKR2014006754-appb-I000010
Figure PCTKR2014006754-appb-I000011
Figure PCTKR2014006754-appb-I000012
Figure PCTKR2014006754-appb-I000013
Figure PCTKR2014006754-appb-I000014
Figure PCTKR2014006754-appb-I000015
Figure PCTKR2014006754-appb-I000016
Figure PCTKR2014006754-appb-I000017
Figure PCTKR2014006754-appb-I000018
Figure PCTKR2014006754-appb-I000019
Figure PCTKR2014006754-appb-I000020
Figure PCTKR2014006754-appb-I000021
The organic electroluminescent compound of the present disclosure can be prepared by a synthetic method known to one skilled in the art. For example, it can be prepared according to the following reaction scheme 1.
[Reaction Scheme 1]
Figure PCTKR2014006754-appb-I000022
In the above reaction scheme 1, Ar1 to Ar8, L1, L2, m, n, and o to r are as defined in formula 1 above, and Hal represents a halogen.
According to the Buchwald-Hartwig reaction in reaction scheme 1, aryl amine and aryl halide are reacted with each other under a basic condition (e.g. by sodium t-butoxide) to form a carbon-nitrogen bond. The reaction is carried out in an aromatic organic solvent such as toluene or xylene; and is usually performed under reflux by using palladium complex such as a combination of palladium acetate and S-Phos (2-dicyclophosphino-2’,6’-dimethoxyphenyl) as a catalyst.
Furthermore, the present disclosure 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 the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised for an organic electroluminescent device, in addition to the compound of the present disclosure.
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, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound of the present disclosure may be comprised in at least one of the light-emitting layer and the hole transport layer. When used in the hole transport layer, the organic electroluminescent compound of the present disclosure may be comprised as a hole transport material. When used in the light-emitting layer, the organic electroluminescent compound of the present disclosure may be comprised as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present disclosure may further comprise at least one compound other than the organic electroluminescent compound of the present disclosure, as a host material. Furthermore, the organic electroluminescent device may further comprise at least one dopant.
Where the organic electroluminescent compound of the present disclosure is comprised as a host material (a first host material) in a light-emitting layer, another compound may be comprised as a second host material. The weight ratio between the first host material and the second host material is in the range of 1:99 to 99:1.
The second host material may be from any of the known phosphorescent host materials. Specifically, the compound selected from the group consisting of the compounds of formulae 11 to 13 below is preferable as the second host material in view of luminous efficiency.
Figure PCTKR2014006754-appb-I000023
Figure PCTKR2014006754-appb-I000024
Figure PCTKR2014006754-appb-I000025
Wherein, Cz represents the following structure:
Figure PCTKR2014006754-appb-I000026
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 (3- 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, a, and b, each independently, represent an integer of 0 to 4; and where h, i, j, k, a, or b 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, the second host material includes the following:
Figure PCTKR2014006754-appb-I000027
Figure PCTKR2014006754-appb-I000028
Figure PCTKR2014006754-appb-I000029
Figure PCTKR2014006754-appb-I000030
Figure PCTKR2014006754-appb-I000031
Figure PCTKR2014006754-appb-I000032
Figure PCTKR2014006754-appb-I000033
Figure PCTKR2014006754-appb-I000034
Figure PCTKR2014006754-appb-I000035
The dopant for the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant. The phosphorescent dopant for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopant may be preferably selected from the group consisting of compounds represented by the following formulae 101 to 103.
Figure PCTKR2014006754-appb-I000036
wherein L is selected from the following structures:
Figure PCTKR2014006754-appb-I000037
R100 represents hydrogen, or a substituted or unsubstituted (C1-C30)alkyl; 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 cyano, a substituted or unsubstituted (C1-C30)alkoxy, or a substituted or unsubstituted (C3-C30)cycloalkyl; R120 to R123 may be linked to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic 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 to an adjacent substituent(s) to form a (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, e.g. fluorene; R201 to R211, each independently, represent hydrogen, deuterium, a halogen, or a (C1-C30)alkyl unsubstituted or substituted with a halogen; c and d, each independently, represent an integer of 1 to 3; where c or d is an integer of 2 or more, each of R100 may be the same or different; and e represents an integer of 1 to 3.
Specifically, the phosphorescent dopant material includes the following:
Figure PCTKR2014006754-appb-I000038
Figure PCTKR2014006754-appb-I000039
Figure PCTKR2014006754-appb-I000040
Figure PCTKR2014006754-appb-I000041
Figure PCTKR2014006754-appb-I000042
Figure PCTKR2014006754-appb-I000043
Figure PCTKR2014006754-appb-I000044
Figure PCTKR2014006754-appb-I000045
Figure PCTKR2014006754-appb-I000046
Figure PCTKR2014006754-appb-I000047
Figure PCTKR2014006754-appb-I000048
Figure PCTKR2014006754-appb-I000049
Figure PCTKR2014006754-appb-I000050
Figure PCTKR2014006754-appb-I000051
Figure PCTKR2014006754-appb-I000052
Figure PCTKR2014006754-appb-I000053
Figure PCTKR2014006754-appb-I000054
Figure PCTKR2014006754-appb-I000055
Figure PCTKR2014006754-appb-I000056
Figure PCTKR2014006754-appb-I000057
Figure PCTKR2014006754-appb-I000058
According to additional aspect of the present disclosure, a mixture or composition for preparing an organic electroluminescent device is provided. The mixture or composition comprises the compound of the present disclosure, as a host material or a hole transport material. The mixture or composition may be a mixture or composition for preparing a light-emitting layer or a hole transport layer of an organic electroluminescent device.
The organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise a light-emitting layer, which may comprise the mixture or composition for the organic electroluminescent device of the present disclosure.
The organic electroluminescent device of the present disclosure may further comprise, in addition to the compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present disclosure, the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal. The organic layer may further comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device of the present disclosure may emit white light by further comprising at least one light-emitting layer, which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
In the organic electroluminescent device of the present disclosure, preferably, at least one layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device of the present disclosure, a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds, and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present disclosure, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the compound of the present disclosure, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound C-2
Figure PCTKR2014006754-appb-I000059
Preparation of compound 1-1
After introducing 2,2,4-dichlorophenylboronic acid (20 g, 104 mmol), 1-bromo-2-iodobenzene (44 g, 157 mmol), palladium(0) tetrakis(triphenylphosphine) (3.6 g, 3.14 mmol), sodium carbonate (27 g, 262 mmol), toluene 520 mL and ethanol 130 mL into a reaction vessel and adding distilled water 130 mL to the mixture, the mixture was stirred for 6 hours at 120°C. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate. After removing the solvent by a rotary evaporator, the products were purified by column chromatography to obtain compound 1-1(15 g, 50 %).
Preparation of compound 1-3
After introducing compound 1-1 (15 g, 50 mmol) and tetrahydrofuran 170 mL into a reaction vessel, the mixture was cooled to -78°C under nitrogen atmosphere, and n-butyl lithium 21 mL (2.5 M, 52 mmol) was then dropped slowly thereto. The mixture was stirred for 2 hours at -78°C, and fluorenone (9.4 g, 52 mmol) dissolved in tetrahydrofuran 100 mL was then dropped slowly thereto. After the dropping, the mixture was warmed slowly to room temperature, and then additionally stirred for 30 minutes. After adding ammonium chloride aqueous solution to the reaction mixture to terminate the reaction, the mixture was extracted with ethyl acetate. The organic layer was dried with magnesium sulfate, and the solvent was then removed by a rotary evaporator to obtain compound 1-2. After adding acetic acid 500 mL and HCl 0.2 mL to the obtained compound 1-2, the mixture was stirred at 120°C overnight. After removing the solvent by a rotary evaporator, the products were purified by column chromatography to obtain compound 1-3 (13 g, 70 %).
Preparation of compound C-2
After introducing compound 1-3 (7 g, 18.1 mmol), N-phenylbiphenyl-4-amine (10.7 g, 43.6 mmol), tris(dibenzylindeneacetone)dipalladium (1.9 g, 2.18 mmol), S-Phos (2 g, 4.36 mmol), sodium tert-butoxide (6.9 g, 72 mmol), and o-xylene 90 mL into a reaction vessel, the mixture was under reflux for 2 hours. The reaction mixture was cooled to room temperature, and then filtered. The obtained solids were washed with methylene chloride (MC). The filtrate was distilled under reduced pressure, and purified by column chromatography to obtain compound C-2 (12 g, 84 %).
Example 2: Preparation of compound C-29
Figure PCTKR2014006754-appb-I000060
Preparation of compound 2-1
After introducing 2-bromoiodobenzene (29.7 g, 105 mmol), 2,4-dichlorophenyl-4-boronic acid (20 g, 105 mmol), palladium(0) tetrakis(triphenylphosphine) (3.6 g, 3.2 mmol), sodium carbonate (28 g, 263 mmol), toluene 600 mL and ethanol 150 mL into a reaction vessel and adding distilled water 150 mL thereto, the mixture was stirred for 6 hours at 120°C. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 2-1 (19.5 g, 61 %).
Preparation of compound 2-2
After introducing 1-indanone(45 g, 340 mmol), phthalic aldehyde (50 g, 374 mmol), sodium ethoxide (25 mL, 20 wt%, 70 mmol), and ethanol 1 L into a reaction vessel, the mixture was stirred for 5 hours at 120°C. After the reaction, the solution was cooled to room temperature, and the precipitated solids were washed with a small amount of methanol to obtain compound 2-2 (50 g, 64 %).
Preparation of compound 2-4
After introducing compound 2-1 (18.5 g, 61.3 mmol) and tetrahydrofuran 200 mL into a reaction vessel, the mixture was cooled to -78°C under nitrogen atmosphere, and n-butyl lithium 25 mL (2.5 M, 61.3 mmol) was then dropped slowly thereto. After stirring the mixture for 2 hours at -78°C, compound 2-2 dissolved in tetrahydrofuran 200 mL was dropped slowly thereto. After the dropping, the mixture was warmed slowly to room temperature, and then additionally stirred for 30 minutes. After adding ammonium chloride aqueous solution to the reaction mixture to terminate the reaction, the mixture was extracted with ethyl acetate. The organic layer was dried with magnesium sulfate, and the solvent was then removed by a rotary evaporator to obtain compound 2-3. Acetic acid 600 mL and HCl 0.3 mL were added to the obtained compound 2-3, and the mixture was then stirred at 120°C overnight. After removing the solvent by a a rotary evaporator, the products were purified by column chromatography to obtain compound 2-4 (14.3 g, 54 %).
Preparation of compound C-29
After introducing compound 2-4 (12 g, 27.6 mmol), diphenylamine (10.3 g, 60.7 mmol), palladium(II) acetate (0.93 g, 4.14 mmol), 2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl (2.3 g, 5.5 mmol), sodium tert-butoxide (6.6 g, 70 mmol), and o-xylene 150 mL into a reaction vessel, the mixture was under reflux for 8 hours. The reaction mixture was cooled to room temperature, and then filtered. The obtained solids were washed with methylene chloride (MC). The filtrate was distilled under reduced pressure, and purified by column chromatography to obtain compound C-29 (10 g, 53 %).
Example 3: Preparation of compound C-49
Figure PCTKR2014006754-appb-I000061
Preparation of compound 3-1
After introducing 1-bromo-3-iodobenzene (20 g, 164 mol), phenylboronic acid (70 g, 246 mol), palladium(0) tetrakis(triphenylphosphine) (5.7 g, 0.49 mol), sodium carbonate (43 g, 410 mol), toluene 820 mL, and ethanol 200 mL into a reaction vessel, and adding distilled water 200 mL thereto, the mixture was stirred for 6 hours at 120°C. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 3-1 (60 g, 150 %).
Preparation of compound 3-2
After introducing compound 3-1 (60 g, 257 mol), aniline (70 mL, 46 mol), palladium(II) acetate (2.3 g, 103 mol), S-Phos (11 g, 26 mol), and xylene 800 mL into a reaction vessel, the mixture was stirred for 6 hours at 120°C. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 3-2 (26 g, 65 %).
Preparation of compound C-49
After introducing compound 1-3 (6 g, 155 mmol), compound 3-2 (9 g, 373 mmol), tris(dibenzylindeneacetone)dipalladium (1.7 g, 1.87 mmol), S-Phos (1.5 g, 3.73 mmol), sodium tert-butoxide (6.0 g, 62 mmol), and o-xylene 100 mL into a reaction vessel, the mixture was under reflux for 8 hours. The reaction mixture was cooled to room temperature, and then filtered. The obtained solids were washed with methylene chloride (MC). The filtrate was distilled under reduced pressure, and purified by column chromatography to obtain compound C-49 (6.4 g, 51 %).
Example 4: Preparation of compound C-8
Figure PCTKR2014006754-appb-I000062
Preparation of compound 4-1
After introducing 2-bromo-9,9-dimethyl-9H-fluorene (25 g, 91 mol), aniline (10 mL, 109 mmol), palladium(II) acetate (1.03 g, 4.58 mmol), t-butyl phosphine(1.85 g, 9.15 mol), and xylene 500 mL into a reaction vessel, the mixture was stirred for 6 hours at 120°C. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 4-1 (20 g, 76 %).
Preparation of compound C-8
After introducing compound 1-3 (7 g, 18.2 mmol), compound 4-1 (12.4 g, 436 mmol), tris(dibenzylindeneacetone)dipalladium (2.0 g, 2.18 mmol), S-Phos (1.79 g, 4.36 mmol), sodium tert-butoxide (7.0 g, 73 mmol), and o-xylene 120 mL into a reaction vessel, the mixture was under reflux for 8 hours. The reaction mixture was cooled to room temperature, and filtered. The obtained solids were washed with methylene chloride (MC). The filtrate was distilled under reduced pressure, and purified by column chromatography to obtain compound C-8 (4 g, 25 %).
Example 5: Preparation of compound C-40
Figure PCTKR2014006754-appb-I000063
Preparation of compound C-40
After introducing compound 1-3 (5.2 g, 13.5 mmol), 4-(diphenylamino) phenylboronic acid (9.3 g, 32.4 mmol), tris(dibenzylindeneacetone)dipalladium (1.2 g, 1.35 mmol), S-Phos (1.1 g, 2.67 mmol), potassium tert-butoxide (5.3 g, 53.9 mmol), and 1,4-dioxane 70 mL into a reaction vessel, the mixture was under reflux for 9 hours. After the reaction, the mixture was washed with distilled water, and extracted with methylene chloride (MC). The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound C-40 (8.0 g, 77 %).
Compounds C-1 to C-48 were prepared in a similar manner to Examples 1 to 5 above. The physical properties of representative compounds among the prepared compounds are shown in Table 1 below.
[Table 1]
Figure PCTKR2014006754-appb-I000064
[ Device Example 1] OLED using the compound of the present disclosure
OLED was produced using the compound of the present disclosure as follows. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) (Geomatec) was subjected to an ultrasonic washing with acetone and isopropanol, sequentially, and was then 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. Compound C-2 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, 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole 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 1,100 cd/m2 and a current density of 2.4 mA/cm2.
[Device Example 2] OLED using the compound of the present disclosure
OLED was produced in the same manner as in Device Example 1, except that compound C-29 was used to form a hole transport layer having a thickness of 20 nm; and after introducing 7-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-7H-benzo[c]carbazole as a host material and compound D-87 as a dopant into the two cells of the vacuum vapor depositing apparatus, respectively, the two materials were evaporated at different rates, so that the dopant was 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 30 nm on the hole transport layer. The produced OLED showed red emission having a luminance of 1,880 cd/m2 and a current density of 13.2 mA/cm2.
[Device Example 3] OLED using the compound of the present disclosure
OLED was produced in the same manner as in Device Example 1, except that compound C-8 was used to form a hole transport layer having a thickness of 20 nm. The produced OLED showed green emission having a luminance of 1,400 cd/m2 and a current density of 2.9 mA/cm2.
[Device Example 4] OLED using the compound of the present disclosure
OLED was produced in the same manner as in Device Example 1, except that compound C-49 was used to form a hole transport layer having a thickness of 20 nm. The produced OLED showed green emission having a luminance of 2,100 cd/m2 and a current density of 4.4 mA/cm2.
[Device Example 5] OLED using the compound of the present disclosure
OLED was produced in the same manner as in Device Example 2, except that compound C-40 was used to form a hole transport layer having a thickness of 20 nm. The produced OLED showed red emission having a luminance of 2,500 cd/m2 and a current density of 18.0 mA/cm2.
[Comparative Device Example 1] OLED using conventional compounds
OLED was produced in the same manner as in Device Example 1, except that N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was used to form a hole transport layer having a thickness of 20 nm. The produced OLED showed green emission having a luminance of 8,000 cd/m2 and a current density of 20.9 mA/cm2.
[Comparative Device Example 2] OLED using conventional compounds
OLED was produced in the same manner as in Device Example 2, except that N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was used to form a hole transport layer having a thickness of 20 nm. The produced OLED showed red emission having a luminance of 6,000 cd/m2 and a current density of 80.0 mA/cm2.
[Comparative Device Example 3] OLED using conventional compounds
OLED was produced in the same manner as in Device Example 1, except that compound-1 was used to form a hole transport layer having a thickness of 20 nm. The produced OLED showed green emission having a luminance of 9,000 cd/m2 and a current density of 21.5 mA/cm2.
Figure PCTKR2014006754-appb-I000065
[ Comparative Device Example 4] OLED using conventional compounds
OLED was produced in the same manner as in Device Example 2, except that compound-1 was used to form a hole transport layer having a thickness of 20 nm. The produced OLED showed red emission having a luminance of 7,000 cd/m2 and a current density of 62.5 mA/cm2.
Figure PCTKR2014006754-appb-I000066
As confirmed by the Examples and the Device Examples, the organic electroluminescent compound of the present disclosure has high glass transition temperature, and provides higher current efficiency than conventional compounds. The organic electroluminescent device shows excellent luminous efficiency, especially current efficienty by using the organic electroluminescent compound of the present disclosure.

Claims (8)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014006754-appb-I000067
    wherein
    Ar1 to Ar4, 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, 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;
    Ar5 to Ar8, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (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;
    m and n, each independently, represent an integer of 0 to 2; where m or n is 2, each of -N(Ar1)(Ar2) or each of -N(Ar3)(Ar4) may be the same or different;
    m+n is 2;
    where m is 1 or 2, L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; where m is 0, L1 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
    where n is 1 or 2, L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; where n is 0, L2 represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
    o represents 1 or 2; where o is 2, each of Ar5 may be the same or different;
    p, q, and r, each independently, represent an integer of 1 to 4; where p, q, or r is an integer of 2 or more, each of Ar6, each of Ar7, or each of Ar8 may be the same or different;
    provided that ,
    Figure PCTKR2014006754-appb-I000068
    ,
    Figure PCTKR2014006754-appb-I000069
    , and
    Figure PCTKR2014006754-appb-I000070
    (wherein X represents -O-, -S-, -C(R1)(R2)-, or -N(R3)-; R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or R1 and R2 may be linked to each other 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) are excluded; and
    the heterocycloalkyl and heteroaryl(ene), 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 or 3.
    Figure PCTKR2014006754-appb-I000071
    Figure PCTKR2014006754-appb-I000072
    wherein
    Ar1 to Ar4, each independently, represent a substituted or unsubstituted (C6-C30)aryl;
    m and n represent 1; and
    L1, L2, Ar5 to Ar8, and o to r are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 4.
    Figure PCTKR2014006754-appb-I000073
    wherein
    Ar1 and Ar2, each independently, represent a substituted or unsubstituted (C6-C30)aryl;
    L1' represents a substituted or unsubstituted (C6-C30)arylene;
    the two -N(Ar1)(Ar2) are bonded to L1' in meta position; and
    Ar5 to Ar8, and o to r are as defined in claim 1.
  4. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted alkyl, the substituted alkenyl, the substituted alkynyl, the substituted cycloalkyl, the substituted cycloalkenyl, the substituted heterocycloalkyl, the substituted aryl(ene) and the substituted heteroaryl(ene) in Ar1 to Ar8, R1 to R3, L1, and L2, 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 (5- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C3-C30)cycloalkyl, a (3- 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 unsubstituted or substituted with a (C1-C30)alkyl, 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 di(C1-C30)alkyl(C6-C30)aryl, a carboxy, a nitro, and a hydroxy.
  5. The organic electroluminescent compound according to claim 1, wherein Ar1 to Ar4, each independently, represent a substituted or unsubstituted (C6-C20)aryl; Ar5 to Ar8, each independently, represet hydrogen, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3- to 20-membered), mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; where m is 1 or 2, L1 represents a single bond or an unsubstituted (C6-C20)arylene; where m is 0, L1 represents hydrogen; where n is 1 or 2, L2 represents a single bond or an unsubstituted (C6-C20)arylene; and where n is 0, L2 represents hydrogen.
  6. The organic electroluminescent compound according to claim 1, wherein Ar1 to Ar4, each independently, represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C15)aryl, or a di(C1-C6)alkyl(C6-C15)aryl; Ar5 to Ar8, each independently, represent hydrogen, or may be linked to an adjacent substituent(s) to form a (3- to 15-membered), mono- or polycyclic, aromatic ring unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C15)aryl, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; where m is 1 or 2, L1 represents a single bond or an unsubstituted (C6-C15)arylene; where m is 0, L1 represents hydrogen; where n is 1 or 2, L2 represents a single bond or an unsubstituted (C6-C15)arylene; and where n is 0, L2 represents hydrogen.
  7. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is selected from the group consisting of:
    Figure PCTKR2014006754-appb-I000074
    Figure PCTKR2014006754-appb-I000075
    Figure PCTKR2014006754-appb-I000076
    Figure PCTKR2014006754-appb-I000077
    Figure PCTKR2014006754-appb-I000078
    Figure PCTKR2014006754-appb-I000079
    Figure PCTKR2014006754-appb-I000080
    Figure PCTKR2014006754-appb-I000081
    Figure PCTKR2014006754-appb-I000082
    Figure PCTKR2014006754-appb-I000083
    Figure PCTKR2014006754-appb-I000084
    Figure PCTKR2014006754-appb-I000085
    Figure PCTKR2014006754-appb-I000086
    Figure PCTKR2014006754-appb-I000087
  8. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
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