WO2015037965A1 - Novel organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

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

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WO2015037965A1
WO2015037965A1 PCT/KR2014/008610 KR2014008610W WO2015037965A1 WO 2015037965 A1 WO2015037965 A1 WO 2015037965A1 KR 2014008610 W KR2014008610 W KR 2014008610W WO 2015037965 A1 WO2015037965 A1 WO 2015037965A1
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substituted
unsubstituted
alkyl
aryl
membered
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PCT/KR2014/008610
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French (fr)
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Hee-Ryong Kang
Young-Gil Kim
Mi-Ja Lee
Nam-Kyun Kim
Young-Jun Cho
Chi-Sik Kim
Kyung-Joo Lee
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority claimed from KR1020130121120A external-priority patent/KR102251474B1/en
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Priority to CN201480046126.0A priority Critical patent/CN105473593A/en
Publication of WO2015037965A1 publication Critical patent/WO2015037965A1/en

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    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to novel organic electroluminescent compounds and organic electroluminescent device comprising the same.
  • An electroluminescence 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].
  • An organic EL device generally has a structure comprising an anode, a cathode, and an organic layer between the anode and the cathode, and a light emission occurs by the recombination of a hole and an electron injected from the anode and the cathode.
  • the organic layer of an organic EL device may be comprised of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc., and the materials used for the organic layer are categorized into hole injection material, hole transport material, light-emitting material, electron transport material, electron injection material, etc.
  • the most important factor determining luminous efficiency in an organic EL device is the light-emitting material.
  • a light-emitting material must have high quantum efficiency, high electron and hole mobility, and the formed light-emitting material layer must be uniform and stable.
  • Light-emitting materials are categorized into blue, green, and red light-emitting materials dependent on the color of the light emission. In addition, there are also yellow and green light-emitting materials.
  • Light-emitting materials can also be categorized into fluorescent (singlet state) light-emitting materials and phosphorescent (triplet state) light-emitting materials dependent on the state of excitation. Fluorescent light-emitting materials had been mainly used in the organic EL devices in the early stage.
  • 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.
  • a light-emitting material can be used as a combination of a host and a dopant to improve color purity, luminous efficiency, and stability. Since host materials greatly influence the efficiency and performance of the EL device when using a dopant/host material system as a light emitting material, their selection is important. 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.
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • 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
  • 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.
  • Korean Patent No. 1219492 discloses an organic electroluminescent compound comprising a specific structure of a fused heterocyclic moiety.
  • the present inventors found that the performance of the device comprising the compound of the present invention is better by experimenting with the electroluminescent devices comprising the compound disclosed in the above reference.
  • the present inventors found that the compound of the present invention can provide not only a device of high luminous efficiency and excellent performance, but also an increase of thermal stability by lowering the evaporation temperature due to low molecular weight and improvement in synthesis method.
  • the first objective of the present invention is to provide an organic electroluminescent compound which has high luminous efficiency
  • the second objective is to provide an organic EL device comprising said compound which has long operational lifespan and improved power and current efficiencies.
  • L 1 represents a single bond, a substituted or unsubstituted (3- to 30-membered)heteroarylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (C1-C30)alkylene;
  • X 1 represents NR 5 , CR 6 R 7 , O, or S, with a proviso that where Y 1 represents N, X 1 is not S;
  • X 2 to X 5 each independently represent CR 8 or N;
  • Y 1 and Y 2 each independently represent CR 9 or N;
  • R 1 to R 4 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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, a substituted or unsubstituted (3- to 30-membered)heteroaryl, -NR 10 R 11 , or -SiR 12 R 13 R 14 ;
  • R 1 , R 2 , and R 3 may be linked to an adjacent substituent(s) to form a mono- or polycyclic, (C3-C30) alicyclic or aromatic ring;
  • R 5 to R 9 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 (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR 10 R 11 , -SiR 12 R 13 R 14 , a cyano, a nitro, or a hydroxyl;
  • R 10 and R 11 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 12 to R 14 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 substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring;
  • the carbon atom(s) of the alicyclic or aromatic ring may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • a, b, c, and d each independently represent an integer of 1 to 4; where a, b, c, or d is an integer of 2 or more, each of R 1 , each of R 2 , each of R 3 , and each of R 4 may be the same or different.
  • the organic electroluminescent compound according to the present invention has high luminous efficiency and good material lifespan characteristics.
  • An organic electroluminescent device comprising the compound provides long operational lifespan and excellent current and power 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.
  • (C1-C30)alkyl(ene) is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.;
  • (C2-C30)alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl is meant to be a linear or branched alkynyl having 2 to 30 carbon atoms
  • 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 compound represented by formula 1 can be represented by formula 2:
  • Y 2 is CR 9 ; and L 1 , X 1 to X 5 , R 1 to R 4 , a, b, c, and d are as defined in formula 1.
  • the compound represented by formula 1 can be represented by formula 3:
  • Y 1 is CR 9 ; and L 1 , X 1 to X 5 , R 1 to R 4 , a, b, c, and d are as defined in formula 1.
  • the compound represented by formula 1 can be represented by formula 4:
  • Y 1 and Y 2 are CR 9 ; X 2 to X 4 are CR 8 ; and L 1 , X 1 , R 1 to R 4 , a, b, c, and d are as defined in formula 1.
  • L 1 represents a single bond, or a substituted or unsubstituted (C6-C30)arylene;
  • R 1 to R 4 each independently represent hydrogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -NR 10 R 11 ;
  • R 5 to R 9 each independently represent hydrogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and
  • R 10 and R 11 each independently represent a substituted or unsubstituted (C6-C30)aryl.
  • the compounds represented by formula 1 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 , X 1 to X 5 , Y 1 , Y 2 , R 1 to R 4 , a, b, c, and d are as defined in formula 1 above.
  • Another embodiment of 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 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 of formula 1 can be comprised in the light-emitting layer as a host material.
  • the light-emitting layer can further comprise one or more dopants, and, if necessary, it may further comprise another compound as a second host material other than the organic electroluminescent compound of formula 1.
  • Another embodiment of the present invention provides a material for producing organic electroluminescent devices.
  • the material comprises first and second host materials, and the first host material comprises the organic electroluminescent compound of the present invention.
  • the ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
  • the second host material can be from any of the known phosphorescent hosts. Hosts selected from the group consisting of the compounds of formulae 5 to 9 below is preferable.
  • X represents O or S
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl, or -SiR 25 R 26 R 27 ; or may be linked to an adjacent substituent(s) to form a (5- 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;
  • 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 3 and Y 4 each independently represent O, S, N(R 31 ), or C(R 32 )(R 33 ), provided that Y 3 and Y 4 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; or may be linked to an adjacent substituent(s) to form a (5- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and R 32 and R 33 may be the same or different;
  • h and i each independently represent an integer of 1 to 3;
  • j, k, l and m each independently represent an integer of 0 to 4.
  • each 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 second host material are as follows:
  • the dopant 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 dopant comprised in the organic electroluminescent device of the present invention may be selected from compounds represented by the following formulae 10 to 12.
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, 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 substituted or unsubstituted (C3-C30)cycloalkyl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy; and adjacent substituents of R 120 to R 123 may be linked to each other to form a fused ring, e.g. quinoline;
  • 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 groups, adjacent substituents may be linked to each other to form a fused ring, e.g. fluorene;
  • 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;
  • 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:
  • composition for 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 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 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 organic electroluminescent 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 (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1' -([1,1'-biphenyl]-4,4'-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzen-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • compound H-90 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material
  • compound D-88 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates and were deposited in a doping amount of 4 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. 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 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the produced OLED device showed a red emission having a luminance of 980 cd/m 2 and a current density of 14.6 mA/cm 2 at a driving voltage of 3.5 V.
  • the time period for the luminance to be dropped to 90% at 5000 nit was 100 hours or more.
  • Comparative Example 1 Production of an OLED device using conventional
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound C-1 as a host, and compound D-88 as a dopant.
  • the produced OLED device showed a red emission having a luminance of 1000 cd/m 2 and a current density of 15.8 mA/cm 2 at a driving voltage of 3.6 V.
  • the time period for the luminance to be dropped to 90% at 5000 nit was 80 hours or more.
  • an organic electroluminescent device having excellent luminous efficiency, long driving lifespan, and improved current and power efficiencies can be prepared.

Abstract

The present invention relates to an organic electroluminescent compound of formula 1 (variables as defined herein) and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present invention can be used in a light-emitting layer and has high luminous efficiency. Thus, an organic electroluminescent device having a long driving lifespan and improved current and power efficiencies can be prepared by using the organic, electroluminescent compound according to the present invention.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to novel organic electroluminescent compounds and organic electroluminescent device comprising the same.
An electroluminescence 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].
An organic EL device generally has a structure comprising an anode, a cathode, and an organic layer between the anode and the cathode, and a light emission occurs by the recombination of a hole and an electron injected from the anode and the cathode. The organic layer of an organic EL device may be comprised of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc., and the materials used for the organic layer are categorized into hole injection material, hole transport material, light-emitting material, electron transport material, electron injection material, etc.
The most important factor determining luminous efficiency in an organic EL device is the light-emitting material. A light-emitting material must have high quantum efficiency, high electron and hole mobility, and the formed light-emitting material layer must be uniform and stable. Light-emitting materials are categorized into blue, green, and red light-emitting materials dependent on the color of the light emission. In addition, there are also yellow and green light-emitting materials. Light-emitting materials can also be categorized into fluorescent (singlet state) light-emitting materials and phosphorescent (triplet state) light-emitting materials dependent on the state of excitation. Fluorescent light-emitting materials had been mainly used in the organic EL devices in the early stage. However, since phosphorescent materials enhance the efficiency for changing light into electricity, i.e. luminous efficiency by four (4) times compared to fluorescent materials, and power consumption can be decreased to increase the lifespan relatively, 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.
A light-emitting material can be used as a combination of a host and a dopant to improve color purity, luminous efficiency, and stability. Since host materials greatly influence the efficiency and performance of the EL device when using a dopant/host material system as a light emitting material, their selection is important. 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 phosphorescent host materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of 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, 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, in order to realize the superior characteristics of an organic EL device, appropriate selection of materials consisting of the organic layers in the device, especially a host or dopant consisting of the light-emitting material must be made. Korean Patent No. 1219492 discloses an organic electroluminescent compound comprising a specific structure of a fused heterocyclic moiety. However, the present inventors found that the performance of the device comprising the compound of the present invention is better by experimenting with the electroluminescent devices comprising the compound disclosed in the above reference.
As a result of researching an organic electroluminescent compound which can provide better performance of an EL device than the compounds disclosed in the above reference, the present inventors found that the compound of the present invention can provide not only a device of high luminous efficiency and excellent performance, but also an increase of thermal stability by lowering the evaporation temperature due to low molecular weight and improvement in synthesis method.
The first objective of the present invention is to provide an organic electroluminescent compound which has high luminous efficiency, and the second objective is to provide an organic EL device comprising said compound which has long operational lifespan and improved power and current efficiencies.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2014008610-appb-I000001
wherein
L1 represents a single bond, a substituted or unsubstituted (3- to 30-membered)heteroarylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (C1-C30)alkylene;
X1 represents NR5, CR6R7, O, or S, with a proviso that where Y1 represents N, X1 is not S;
X2 to X5 each independently represent CR8 or N;
Y1 and Y2 each independently represent CR9 or N;
R1 to R4 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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, a substituted or unsubstituted (3- to 30-membered)heteroaryl, -NR10R11, or -SiR12R13R14;
R1, R2, and R3 may be linked to an adjacent substituent(s) to form a mono- or polycyclic, (C3-C30) alicyclic or aromatic ring;
R5 to R9 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 (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR10R11, -SiR12R13R14, a cyano, a nitro, or a hydroxyl;
R10 and R11 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;
R12 to R14 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 substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring;
the carbon atom(s) of the alicyclic or aromatic ring may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
the heteroaryl(ene) and the heterocycloalkyl each independently contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P; and
a, b, c, and d each independently represent an integer of 1 to 4; where a, b, c, or d is an integer of 2 or more, each of R1, each of R2, each of R3, and each of R4 may be the same or different.
The organic electroluminescent compound according to the present invention has high luminous efficiency and good material lifespan characteristics. An organic electroluminescent device comprising the compound provides long operational lifespan and excellent current and power 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.
Herein, “(C1-C30)alkyl(ene)” is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “(C2-C30)alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.; “(C2-C30)alkynyl” is 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, preferably 5 to 7, 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, fluorenyl, phenanthrenyl, 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, preferably 3 to 20, and more preferably 3 to 15, 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, benzoimidazolyl, 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.
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(ene), the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (3- to 30-membered)heteroaryl(ene), the substituted (C6-C30)aryl(C1-C30)alkyl, and the substituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring in L1, and R1 to R14 in 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.
The compound represented by formula 1 can be represented by formula 2:
Figure PCTKR2014008610-appb-I000002
wherein
Y2 is CR9; and L1, X1 to X5, R1 to R4, a, b, c, and d are as defined in formula 1.
The compound represented by formula 1 can be represented by formula 3:
Figure PCTKR2014008610-appb-I000003
wherein
Y1 is CR9; and L1, X1 to X5, R1 to R4, a, b, c, and d are as defined in formula 1.
The compound represented by formula 1 can be represented by formula 4:
Figure PCTKR2014008610-appb-I000004
wherein
Y1 and Y2 are CR9; X2 to X4 are CR8; and L1, X1, R1 to R4, a, b, c, and d are as defined in formula 1.
In formulae 1 to 4 above, preferably, L1 represents a single bond, or a substituted or unsubstituted (C6-C30)arylene; R1 to R4 each independently represent hydrogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -NR10R11; R5 to R9 each independently represent hydrogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and R10 and R11 each independently represent a substituted or unsubstituted (C6-C30)aryl.
The compounds represented by formula 1 include the following compounds, but are not limited thereto:
Figure PCTKR2014008610-appb-I000005
Figure PCTKR2014008610-appb-I000006
Figure PCTKR2014008610-appb-I000007
Figure PCTKR2014008610-appb-I000008
Figure PCTKR2014008610-appb-I000009
Figure PCTKR2014008610-appb-I000010
Figure PCTKR2014008610-appb-I000011
Figure PCTKR2014008610-appb-I000012
Figure PCTKR2014008610-appb-I000013
Figure PCTKR2014008610-appb-I000014
Figure PCTKR2014008610-appb-I000015
Figure PCTKR2014008610-appb-I000016
Figure PCTKR2014008610-appb-I000017
Figure PCTKR2014008610-appb-I000018
Figure PCTKR2014008610-appb-I000019
Figure PCTKR2014008610-appb-I000020
Figure PCTKR2014008610-appb-I000021
Figure PCTKR2014008610-appb-I000022
Figure PCTKR2014008610-appb-I000023
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 PCTKR2014008610-appb-I000024
wherein L1, X1 to X5, Y1, Y2, R1 to R4, a, b, c, and d are as defined in formula 1 above.
Another embodiment of 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 compound of formula 1.
One of the first and second electrodes is an anode, and the other is 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 of formula 1 can be comprised in the light-emitting layer as a host material. Preferably, the light-emitting layer can further comprise one or more dopants, and, if necessary, it may further comprise another compound as a second host material other than the organic electroluminescent compound of formula 1.
Another embodiment of the present invention provides a material for producing organic electroluminescent devices. The material comprises first and second host materials, and the first host material comprises the organic electroluminescent compound of the present invention. Herein, the ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
The second host material can be from any of the known phosphorescent hosts. Hosts selected from the group consisting of the compounds of formulae 5 to 9 below is preferable.
Figure PCTKR2014008610-appb-I000025
Figure PCTKR2014008610-appb-I000026
Figure PCTKR2014008610-appb-I000027
Figure PCTKR2014008610-appb-I000028
Figure PCTKR2014008610-appb-I000029
wherein Cz represents the following structure;
Figure PCTKR2014008610-appb-I000030
X represents O or S;
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 (5- to 30-membered)heteroaryl, or -SiR25R26R27; or may be linked to an adjacent substituent(s) to form a (5- 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;
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;
Y3 and Y4 each independently represent O, S, N(R31), or C(R32)(R33), provided that Y3 and Y4 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; or may be linked to an adjacent substituent(s) to form a (5- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and R32 and R33 may be the same or different;
h and i each independently represent an integer of 1 to 3;
j, k, l and m each independently represent an integer of 0 to 4; and
where h, i, j, k, l or m is an integer of 2 or more, each of (Cz-L4), 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 second host material are as follows:
Figure PCTKR2014008610-appb-I000031
Figure PCTKR2014008610-appb-I000032
Figure PCTKR2014008610-appb-I000033
Figure PCTKR2014008610-appb-I000034
Figure PCTKR2014008610-appb-I000035
Figure PCTKR2014008610-appb-I000036
Figure PCTKR2014008610-appb-I000037
Figure PCTKR2014008610-appb-I000038
Figure PCTKR2014008610-appb-I000039
Figure PCTKR2014008610-appb-I000040
Figure PCTKR2014008610-appb-I000041
Figure PCTKR2014008610-appb-I000042
Figure PCTKR2014008610-appb-I000043
Figure PCTKR2014008610-appb-I000044
Figure PCTKR2014008610-appb-I000045
Figure PCTKR2014008610-appb-I000046
Figure PCTKR2014008610-appb-I000047
Figure PCTKR2014008610-appb-I000048
[wherein TPS represents triphenylsilyl]
The dopant 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 dopant comprised in the organic electroluminescent device of the present invention may be selected from compounds represented by the following formulae 10 to 12.
Figure PCTKR2014008610-appb-I000049
Figure PCTKR2014008610-appb-I000050
Figure PCTKR2014008610-appb-I000051
wherein L is selected from the following structures:
Figure PCTKR2014008610-appb-I000052
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 substituted or unsubstituted (C3-C30)cycloalkyl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy; and adjacent substituents of R120 to R123 may be linked to each other to form a fused ring, e.g. quinoline;
R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where R124 to R127 are aryl groups, adjacent substituents may be linked to each other to form a fused ring, e.g. fluorene;
R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl;
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 PCTKR2014008610-appb-I000053
Figure PCTKR2014008610-appb-I000054
Figure PCTKR2014008610-appb-I000055
Figure PCTKR2014008610-appb-I000056
Figure PCTKR2014008610-appb-I000057
Figure PCTKR2014008610-appb-I000058
Figure PCTKR2014008610-appb-I000059
Figure PCTKR2014008610-appb-I000060
Figure PCTKR2014008610-appb-I000061
Figure PCTKR2014008610-appb-I000062
Figure PCTKR2014008610-appb-I000063
Figure PCTKR2014008610-appb-I000064
Figure PCTKR2014008610-appb-I000065
Figure PCTKR2014008610-appb-I000066
Figure PCTKR2014008610-appb-I000067
Figure PCTKR2014008610-appb-I000068
Figure PCTKR2014008610-appb-I000069
Figure PCTKR2014008610-appb-I000070
Figure PCTKR2014008610-appb-I000071
Figure PCTKR2014008610-appb-I000072
Figure PCTKR2014008610-appb-I000073
In another embodiment of the present invention, a composition for 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 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.
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 organic electroluminescent 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 H-1
Figure PCTKR2014008610-appb-I000074
Figure PCTKR2014008610-appb-I000075
Preparation of compound 2-1
After adding 1,4-dibromonaphthalene (50 g, 174.8 mmol), pinacol diborane (98 g, 391.6 mmol), bis(triphenylphosphine)palladium(II) dichloride [PdCl2(PPh3)2] (12 g, 17.8 mmol), potassium acetate (KOAc) (76 g, 769.1 mmol), and tetrahydrofuran (THF) 1 L in a flask, the mixture was stirred under reflux for 5 hours. After completing the reaction, an organic layer was extracted with ethyl acetate (EA), and the remaining moisture was removed using magnesium sulfate. The obtained solid was dried and separated with column chromatography to obtain compound 2-1 (60 g, 94%).
Preparation of compound 2-2
After adding compound 2-1 (60 g, 157.8 mmol), 1-bromo-2-nitrobenzene (96 g, 473.4 mmol), tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4] (18.3 g, 15.7 mmol), 2 M Na2CO3 240 mL, ethanol (EtOH) 240 mL, and toluene 500 mL in a flask, the mixture was stirred under reflux at 120°C for 5 hours. After completing the reaction, an organic layer was extracted with ethyl acetate (EA), and the remaining moisture was removed using magnesium sulfate. The obtained solid was dried and separated with column chromatography to obtain compound 2-2 (50 g, 85%).
Preparation of compound 2-3
After adding compound 2-2 (43 g, 116.1 mmol), triphenylphosphine (PPh3) (61 g, 232.2 mmol), and dichlorobenzene (DCB) 600 mL in a flask, the mixture was stirred under reflux at 150°C for 5 hours. After completing the reaction, the mixture was distilled, and pulverized with MeOH to obtain compound 2-3 (22 g, 56%).
Preparation of compound 2-4
After adding compound 2-3 (22 g, 65.0 mmol), iodobenzene (11 mL, 97.5 mmol), CuI (6.2 g, 32.5 mmol), K3PO4 (42 g, 195 mmol), ethylenediamine (EDA) (9 mL, 130 mmol), and toluene 300 mL in a flask, the mixture was stirred under reflux at 120°C for 5 hours. After completing the reaction, an organic layer was extracted with ethyl acetate (EA), and the remaining moisture was removed using magnesium sulfate. The obtained solid was dried and separated with column chromatography to obtain compound 2-4 (18 g, 67%).
Preparation of compound 2-5
After adding compound 2-4 (18 g, 43.4 mmol), PPh3 (25 g, 108.5 mmol), and DCB 220 mL in a flask, the mixture was stirred under reflux at 150°C for 5 hours. After completing the reaction, the mixture was distilled, and pulverized with MeOH to obtain compound 2-5 (11 g, 70%).
Preparation of compound H-1
After dissolving compound 2-5 (4 g, 10.47 mmol) and compound 1-9 (4.2 g, 15.7 mmol) in dimethylformamide (DMF) 50 mL, NaH (0.6 g, 15.71 mmol, 60% in mineral oil) was added to the mixture. The mixture was then stirred for 12 hours at room temperature, and methanol and distilled water were added thereto. The obtained solid was filtered under reduced pressure, and separated with column chromatography to obtain compound H-1 (4.2 g, 65%).
Example 2: Preparation of compound H-62
Figure PCTKR2014008610-appb-I000076
Figure PCTKR2014008610-appb-I000077
Preparation of compound 3-1
After adding compound 2-2 (55 g, 0.148 mol), PPh3 (78 g, 0.297 mol), and DCB 1100 mL in a flask, the reaction mixture was heated to 190°C and stirred for 5 hours. After completing the reaction, DCB was removed using a distiller, the mixture was washed with distilled water, extracted with EA, the organic layer was dried with MgSO4, and the solvent was removed using a rotary evaporator. Thereafter, the obtained solid was purified with column chromatography to obtain compound 3-1 (35 g, 78%).
Preparation of compound 3-2
After adding compound 3-1 (9.4 g, 0.031 mol), iodobenzene (6.3 g, 0.031 mol), CuI (2.95 g, 0.015 mol), K2CO3 (4.3 g, 0.031 mol), and EDA (2 mL, 0.031 mol) in a flask, the reaction mixture was heated to 120°C and stirred for 5 hours. After completing the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried with MgSO4, and the solvent was removed using a rotary evaporator. Thereafter, the obtained solid was purified with column chromatography to obtain compound 3-2 (11 g, 93%).
Preparation of compound 3-3
After adding compound 3-2 (11 g, 0.030 mol), 1-bromo-4-iodobenzene (17 g, 0.060 mol), Cu (5.7 g, 0.090 mol), K2CO3 (21 g, 0.150 mol), 18-Crown-6 (1.6 g, 0.006 mol), and DCB 115 mL in a flask, the reaction mixture was heated to 190°C and stirred for 12 hours. DCB was then removed using a distiller, the mixture was washed with distilled water, extracted with EA, the organic layer was dried with MgSO4, and the solvent was removed using a rotary evaporator. Thereafter, the obtained solid was purified with column chromatography to obtain compound 3-3 (14 g, 87%).
Preparation of compound 3-4
After adding compound 3-3 (14 g, 0.026 mol) in a flask under nitrogen atmosphere, THF 200 mL was added, and the mixture was stirred at -78°C for 20 minutes. Thereafter, n-butyl lithium (n-BuLi) (2.5 M) (12.5 mL, 0.031 mol) was slowly added to the flask, and the mixture was stirred at -78°C for 40 minutes. 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8 mL, 0.039 mol) was then added to the flask, and the mixture was stirred for 12 hours at room temperature. After completing the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried with MgSO4, and the solvent was removed using a rotary evaporator. Thereafter, the obtained solid was purified with column chromatography to obtain compound 3-4 (11 g, 73%).
Preparation of compound H-62
After adding compound 3-4 (2 g, 0.003 mol), compound 1-9 (784 mg, 0.003 mol), Pd(PPh3)4 (230 mg, 0.23 mmol), K2CO3 (2 M, 5 mL), EtOH 5 mL, and toluene 10 mL in a flask, the reaction mixture was heated to 120°C and stirred for 7 hours. After completing the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried with MgSO4, and the solvent was removed using a rotary evaporator. Thereafter, the obtained solid was purified with column chromatography to obtain compound H-62 (1.5 g, 71%).
Example 3: Preparation of compound H-13
Figure PCTKR2014008610-appb-I000078
After adding compound 4-1 (14 g, 0.043 mol), compound 4-2 (18.4 g, 0.065 mol), CuI (4.1 g, 0.021 mol), ethylenediamine (2.9 mL, 0.043 mol), Cs2CO3 (27.5 g, 0.129 mol), and toluene 400 mL in a flask, the mixture was stirred at 120°C for 12 hours. After completing the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried with MgSO4, and the solvent was removed using a rotary evaporator. Thereafter, the obtained solid was purified with column chromatography to obtain compound H-13 (8.5 g, 43%).
Example 4: Preparation of compound H-90
Figure PCTKR2014008610-appb-I000079
Preparation of compound 5-2
After adding compound 4-1 (14 g, 0.043 mol), compound 5-1 (18.4 g, 0.065 mol), CuI (4.1 g, 0.021 mol), ethylenediamine (2.9 mL, 0.043 mol), Cs2CO3 (27.5 g, 0.129 mol), and toluene 400 mL in a flask, the mixture was stirred at 120°C for 12 hours. After completing the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried with MgSO4, and the solvent was removed using a rotary evaporator. Thereafter, the obtained solid was purified with column chromatography to obtain compound 5-2 (8.5 g, 43%).
Preparation of compound 5-3
After adding compound 5-2 (7.3 g, 0.015 mol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane (5.9 g, 0.023 mol), potassium acetate (3.8 g, 0.038 mol), PdCl2(PPh3)2 (561 mg, 0.008 mol), and 1,4-dioxane 70 mL in a flask, the reaction mixture was heated to 150°C and stirred for 5 hours. After completing the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried with MgSO4, and the solvent was removed using a rotary evaporator. Thereafter, the obtained solid was purified with column chromatography to obtain compound 5-3 (5.0 g, 68%).
Preparation of compound H-90
After adding compound 5-3 (2.5 g, 0.0048 mol), compound 4-2 (1.0 g, 0.0044 mol), Pd(PPh3)4 (230 mg, 0.0005 mmol), K2CO3 (2 M, 6.3 mL), EtOH 6.3 mL, and toluene 13 mL in a flask, the reaction mixture was heated to 120°C and stirred for 7 hours. After completing the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried with MgSO4, and the solvent was removed using a rotary evaporator. Thereafter, the obtained solid was purified with column chromatography to obtain compound H-90 (2.1 g, 84%).
Example 5: Preparation of compound H-9
Figure PCTKR2014008610-appb-I000080
Preparation of compound 6-2
After dissolving compound 6-1 (15 g, 94.23 mmol), 2-chloroiodobenzene (12.6 mL, 103.65 mmol), palladium(II)acetate [Pd(OAc)2] (0.84 g, 3.76 mmol), 50% t-butylphosphine (3.6 mL, 7.53 mmol), and sodium t-butoxide (22.6 g, 235.57 mmol) in toluene 480 mL in a flask, the mixture was stirred under reflux at 120°C for 4 hours. After completing the reaction, the mixture was extracted with dichloromethane/purified water, and separated with column chromatography to obtain compound 6-2 (10.4 g, 41%).
Preparation of compound 6-3
After dissolving compound 6-2 (9.4 g, 34.93 mmol), 2-chloroiodobenzene (4.25 mL, 34.93 mmol), Cu2O (1.5 g, 10.48 mmol), picolinic acid (2.6 g, 20.96 mmol), and cesium carbonate (23 g, 69.87 mmol) in acetonitrile 170 mL, the mixture was stirred under reflux at 100°C for 12 hours. After completing the reaction, the mixture was extracted with dichloromethane, and separated with column chromatography to obtain compound 6-3 (4 g, 30%).
Preparation of compound 6-4
After dissolving compound 6-3 (4 g, 10.55 mmol), Pd(OAc)2 (0.23 g, 1.055 mmol), ligand (0.77 g, 2.11 mmol), and potassium carbonate (13.7 g, 42.2 mmol) in N-methylpyrrolidone 50 mL, the mixture was stirred under reflux at 220°C for 3 hours. After completing the reaction, the mixture was extracted with dichloromethane/purified water, and separated with column chromatography to obtain compound 6-4 (2.5 g, 78%).
Preparation of compound H-9
After dissolving compound 6-4 (4 g, 13.01 mmol) and compound 4-2 (3.1 g, 13.01 mmol) in dimethylformamide (DMF) 50 mL, NaH (1.56 g, 39.03 mmol, 60% in mineral oil) was added to the mixture. The mixture was then stirred for 12 hours at room temperature, and methanol and distilled water were added thereto. The obtained solid was filtered under reduced pressure, and separated with column chromatography to obtain compound H-9 (1.7 g, 25.5%).
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 (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1'-([1,1'-biphenyl]-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzen-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. Then, N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl 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 hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound H-90 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-88 was introduced into another cell as a dopant. The two materials were evaporated at different rates and were deposited in a doping amount of 4 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. 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 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
The produced OLED device showed a red emission having a luminance of 980 cd/m2 and a current density of 14.6 mA/cm2 at a driving voltage of 3.5 V. The time period for the luminance to be dropped to 90% at 5000 nit was 100 hours or more.
Comparative Example 1: Production of an OLED device using conventional
organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 1, except for using compound C-1
Figure PCTKR2014008610-appb-I000081
as a host, and compound D-88 as a dopant.
The produced OLED device showed a red emission having a luminance of 1000 cd/m2 and a current density of 15.8 mA/cm2 at a driving voltage of 3.6 V. The time period for the luminance to be dropped to 90% at 5000 nit was 80 hours or more.
By using the organic electroluminescent compound according to the present invention, an organic electroluminescent device having excellent luminous efficiency, long driving lifespan, and improved current and power efficiencies can be prepared.

Claims (8)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014008610-appb-I000082
    wherein
    L1 represents a single bond, a substituted or unsubstituted (3- to 30-membered)heteroarylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (C1-C30)alkylene;
    X1 represents NR5, CR6R7, O, or S, with a proviso that where Y1 represents N, X1 is not S;
    X2 to X5 each independently represent CR8 or N;
    Y1 and Y2 each independently represent CR9 or N;
    R1 to R4 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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, a substituted or unsubstituted (3- to 30-membered)heteroaryl, -NR10R11, or -SiR12R13R14;
    R1, R2, and R3 may be linked to an adjacent substituent(s) to form a mono- or polycyclic, (C3-C30) alicyclic or aromatic ring;
    R5 to R9 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 (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR10R11, -SiR12R13R14, a cyano, a nitro, or a hydroxyl;
    R10 and R11 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;
    R12 to R14 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 substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring;
    the carbon atom(s) of the alicyclic or aromatic ring may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    the heteroaryl(ene) and the heterocycloalkyl each independently contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P; and
    a, b, c, and d each independently represent an integer of 1 to 4; where a, b, c, or d is an integer of 2 or more, each of R1, each of R2, each of R3, and each of R4 may be the same or different.
  2. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 2:
    Figure PCTKR2014008610-appb-I000083
    wherein
    Y2 is CR9; and L1, X1 to X5, R1 to R4, a, b, c, and d are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 3:
    Figure PCTKR2014008610-appb-I000084
    wherein
    Y1 is CR9; and L1, X1 to X5, R1 to R4, a, b, c, and d are as defined in claim 1.
  4. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 4:
    Figure PCTKR2014008610-appb-I000085
    wherein
    Y1 and Y2 are CR9; X2 to X4 are CR8; and L1, X1, R1 to R4, a, b, c, and d are as defined in claim 1.
  5. The organic electroluminescent compound according to claim 1, wherein L1 represents a single bond, or a substituted or unsubstituted (C6-C30)arylene; R1 to R4 each independently represent hydrogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -NR10R11; R5 to R9 each independently represent hydrogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and R10 and R11 each independently represent a substituted or unsubstituted (C6-C30)aryl.
  6. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl(ene), the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (3- to 30-membered)heteroaryl(ene), the substituted (C6-C30)aryl(C1-C30)alkyl, and the substituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring in L1, and R1 to R14 are each independently 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.
  7. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of the following compounds:
    Figure PCTKR2014008610-appb-I000086
    Figure PCTKR2014008610-appb-I000087
    Figure PCTKR2014008610-appb-I000088
    Figure PCTKR2014008610-appb-I000089
    Figure PCTKR2014008610-appb-I000090
    Figure PCTKR2014008610-appb-I000091
    Figure PCTKR2014008610-appb-I000092
    Figure PCTKR2014008610-appb-I000093
    Figure PCTKR2014008610-appb-I000094
    Figure PCTKR2014008610-appb-I000095
    Figure PCTKR2014008610-appb-I000096
    Figure PCTKR2014008610-appb-I000097
    Figure PCTKR2014008610-appb-I000098
    Figure PCTKR2014008610-appb-I000099
    Figure PCTKR2014008610-appb-I000100
    Figure PCTKR2014008610-appb-I000101
    Figure PCTKR2014008610-appb-I000102
    Figure PCTKR2014008610-appb-I000103
    Figure PCTKR2014008610-appb-I000104
  8. An organic electroluminescent device comprising the compound according to claim 1.
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WO2017014546A1 (en) * 2015-07-20 2017-01-26 Rohm And Haas Electronic Materials Korea Ltd. Luminescent material for delayed fluorescence and organic electroluminescent device comprising the same
WO2017191896A1 (en) * 2016-05-03 2017-11-09 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
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