WO2016089162A1 - 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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WO2016089162A1
WO2016089162A1 PCT/KR2015/013231 KR2015013231W WO2016089162A1 WO 2016089162 A1 WO2016089162 A1 WO 2016089162A1 KR 2015013231 W KR2015013231 W KR 2015013231W WO 2016089162 A1 WO2016089162 A1 WO 2016089162A1
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substituted
unsubstituted
alkyl
aryl
organic electroluminescent
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Hee-Choon Ahn
Tae-Jin Lee
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Definitions

  • the present invention relates to organic electroluminescent compounds and organic electroluminescent device comprising the same.
  • An electroluminescent device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • the first organic EL device was 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].
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green, and blue materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • an organic EL device has a structure of a multilayer comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.
  • the selection of a compound comprised in the hole transport layer is known as a method for improving the characteristics of a device such as hole transport efficiency to the light-emitting layer, luminous efficiency, lifespan, etc.
  • CuPc copper phthalocyanine
  • NPB 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
  • MTDATA 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine
  • Synthetic Metals Vol. 162 (2012) pp. 2059-2062 discloses a methyl compound substituted with phenyl, diphenylaniline, and dibenzofuran as an organic electroluminescent compound.
  • the above reference does not specifically disclose an organic electroluminescent device using a compound in which at least either one of the two aryls of the diarylamine is not phenyl.
  • the objective of the present invention is to provide an organic electroluminescent compound having excellent luminous properties.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl;
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 3- to 30-membered heteroarylene;
  • X represents O, S, CR 5 R 6 , or NR 7 ;
  • R 1 to R 7 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 8 R 9 , or -SiR 10 R 11 R 12 ; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, whose carbon
  • R 8 to R 12 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, or a substituted or unsubstituted 3- to 30-membered heteroaryl;
  • a represents an integer of 1 to 4, where a is an integer of 2 or more, each of R 1 may be the same or different;
  • b represents an integer of 1 to 3, where b is an integer of 2 or more, each of R 2 may be the same or different;
  • c and d each independently represent an integer of 1 to 5, where c or d is an integer of 2 or more, each of R 3 and each of R 4 may be the same or different;
  • heteroaryl(ene) and heterocycloalkyl each independently contain at least one hetero atom selected from B, N, O, S, Si, and P.
  • an organic electroluminescent device having excellent luminous properties can be produced.
  • 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 is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.;
  • (C2-C30)alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms constituting the chain, 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 substituents of the substituted alkyl, the substituted cycloalkyl, the substituted cycloalkenyl, the substituted heterocycloalkyl, the substituted aryl(ene), the substituted heteroaryl(ene), and the substituted mono- or polycyclic, alicyclic or aromatic ring in Ar 1 , Ar 2 , L 1 , L 2 , and R 1 to R 12 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
  • the compound represented by formula 1 can be represented by one of the following formulas 2 and 3:
  • Ar 1, Ar 2 , L 1 , L 2 , X, R 1 to R 4 , and a to d are as defined in formula 1.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl, where Ar 1 and Ar 2 are not both phenyl; preferably each independently represent a substituted or unsubstituted (C6-C20)aryl; and more preferably each independently represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C25)aryl, a tri(C6-C12)arylsilyl, or a (C1-C6)alkyl(C6-C15)aryl.
  • Ar 1 and Ar 2 may each independently represent one of the following structures:
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 3- to 30-membered heteroarylene; preferably each independently represent a single bond, or a substituted or unsubstituted (C6-C12)arylene; and more preferably each independently represent a single bond, or an unsubstituted (C6-C12)arylene.
  • X represents O, S, CR 5 R 6 , or NR 7 .
  • R 1 to R 7 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 8 R 9 , or -SiR 10 R 11 R 12 ; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, whose carbon
  • R 8 to R 12 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, or a substituted or unsubstituted 3- to 30-membered heteroaryl; preferably each independently represent a substituted or unsubstituted (C6-C12)aryl; and more preferably each independently represent an unsubstituted (C6-C12)aryl.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C20)aryl
  • L 1 and L 2 each independently represent a single bond, or a substituted or unsubstituted (C6-C12)arylene
  • X represents O, S, CR 5 R 6 , or NR 7
  • R 1 to R 7 each independently represent hydrogen, a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C12)aryl.
  • Ar 1 and Ar 2 each independently represent (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C25)aryl, a tri(C6-C12)arylsilyl, or a (C1-C6)alkyl(C6-C15)aryl;
  • L 1 and L 2 each independently represent a single bond, or an unsubstituted (C6-C12)arylene;
  • X represents O, S, CR 5 R 6 , or NR 7 ; and
  • R 1 to R 7 each independently represent hydrogen, an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C12)aryl.
  • the organic electroluminescent compound represented by formula 1 includes the following compounds, but is not limited thereto:
  • the organic electroluminescent compound of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, it can be prepared according to the following reaction scheme.
  • Ar 1 , Ar 2 , L 1 , L 2 , X, R 1 to R 4 , and a to d are as defined in formula 1.
  • the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes.
  • the organic layer may comprise at least one organic electroluminescent compound of formula 1.
  • the organic layer comprises a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the organic electroluminescent compound of the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound of the present invention can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound of the present invention can be comprised as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more host compounds, and can further comprise one or more dopants.
  • the organic electroluminescent compound of the present invention is comprised as a host material (first host material) of the light-emitting layer
  • another compound can be comprised as a second host material.
  • the weight ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
  • the host material of a compound other than the organic electroluminescent compound of the present invention can be any of the known phosphorescent hosts. Specifically, the compound selected from the group consisting of the compounds of formulae 11 to 13 below is preferable in terms of luminous efficiency.
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, or -SiR 25 R 26 R 27 , R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 5- to 30-membered heteroarylene;
  • M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl;
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )-, or -C(R 32 )(R 33 )-, provided that Y 1 and Y 2 do not simultaneously exist;
  • R 31 to R 33 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl, and R 32 and R 33 may be the same or different;
  • h and i each independently represent an integer of 1 to 3;
  • j, k, 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 host material are as follows:
  • TPS represents a triphenylsilyl group
  • the dopant comprised in the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant.
  • the dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper, and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper, and platinum, and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopant is preferably selected from the group consisting of the compounds of formulae 101 to 103 below.
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 , and R 111 to R 123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a cyano, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (C3-C30)cycloalkyl; adjacent substituents of R 106 to R 109 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl; and adjacent substituents of R 120 to R 123 may be linked to each other
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R 124 to R 127 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl, and adjacent substituents of R 208 to R 211 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
  • r and s each independently represent an integer of 1 to 3; where r or s 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 compounds include the following:
  • compositions for preparing an organic electroluminescent device comprises the compound according to the present invention as a host material or a hole transport material.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes.
  • the organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for preparing the organic electroluminescent device according to the present invention.
  • the organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising said metal.
  • the organic layer may further comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if necessary, 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 (including 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 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 comprising the organic electroluminescent compound according to the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water, sequentially, and was then stored in isopropanol.
  • the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 4 ,N 4' -diphenyl-N 4 ,N 4' -bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-diamine (compound HI-1) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a first hole injection layer having a thickness of 80 nm on the ITO substrate.
  • 1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile (compound HI-2) was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 3 nm on the first hole injection layer.
  • N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine (compound HT-1) was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer.
  • Compound C-1 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer.
  • compound H-1 as below was introduced into one cell of the vacuum vapor depositing apparatus as a host, and compound D-96 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates and were deposited in a doping amount of 2 wt% (the amount of dopant) based on the total amount of the dopant and host to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer.
  • the produced OLED device showed a red emission having a luminance of 1000 cd/m 2 and a current density of 3.67 mA/cm 2 .
  • Comparative Example 1 Production of an OLED device comprising
  • An OLED device was produced in the same manner as in Device Example 1, except for depositing N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine (compound HT-1) at a thickness of 60 nm for the second hole transport layer.
  • the produced OLED device showed a red emission having a luminance of 1000 cd/m 2 and a current density of 7.5 mA/cm 2 .
  • the organic electroluminescent compound according to the present invention showed excellent luminous characteristics.
  • the device using the organic electroluminescent compound of the present invention has excellent luminous characteristics.

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Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. By using the organic electroluminescent compound of the present invention, an organic electroluminescent device having excellent luminous properties can be produced.

Description

ORGANIC ELECTROLUMINESCENT COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to organic electroluminescent compounds and organic electroluminescent device comprising the same.
An electroluminescent device (EL device) is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. The first organic EL device was developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in an organic EL device is 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, development of phosphorescent light-emitting materials is widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green, and blue materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known phosphorescent host material. 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.
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, and the lifespan of the device decreases. (2) The power efficiency of an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although an organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Further, the operational lifespan of an organic EL device is short and luminous efficiency is still required to be improved.
Meanwhile, in order to enhance its efficiency and stability, an organic EL device has a structure of a multilayer comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. The selection of a compound comprised in the hole transport layer is known as a method for improving the characteristics of a device such as hole transport efficiency to the light-emitting layer, luminous efficiency, lifespan, etc.
In this regard, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (MTDATA), etc., were used as a hole injection and transport material. However, an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
Therefore, a hole transport layer for improving durability of an organic EL device still needs to be developed.
Synthetic Metals Vol. 162 (2012) pp. 2059-2062 discloses a methyl compound substituted with phenyl, diphenylaniline, and dibenzofuran as an organic electroluminescent compound. However, the above reference does not specifically disclose an organic electroluminescent device using a compound in which at least either one of the two aryls of the diarylamine is not phenyl.
The objective of the present invention is to provide an organic electroluminescent compound having excellent luminous properties.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2015013231-appb-I000001
wherein
Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl;
where Ar1 and Ar2 are not both phenyl;
L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 3- to 30-membered heteroarylene;
X represents O, S, CR5R6, or NR7;
R1 to R7 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, -NR8R9, or -SiR10R11R12; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
R8 to R12 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, or a substituted or unsubstituted 3- to 30-membered heteroaryl;
a represents an integer of 1 to 4, where a is an integer of 2 or more, each of R1 may be the same or different;
b represents an integer of 1 to 3, where b is an integer of 2 or more, each of R2 may be the same or different;
c and d each independently represent an integer of 1 to 5, where c or d is an integer of 2 or more, each of R3 and each of R4 may be the same or different; and
the heteroaryl(ene) and heterocycloalkyl each independently contain at least one hetero atom selected from B, N, O, S, Si, and P.
By using the organic electroluminescent compound of the present invention, an organic electroluminescent device having excellent luminous properties can be produced.
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.
Hereinafter, the organic electroluminescent compound represented by formula 1 will be described in detail.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “(C2-C30)alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms constituting the chain, 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 constituting the chain, 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 ring backbone carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “3- to 7- membered heterocycloalkyl” is a cycloalkyl having 3 to 7 ring backbone atoms, including at least one heteroatom selected from B, N, O, S, 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 ring backbone carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; “5- to 30-membered heteroaryl(ene)” is an aryl having 5 to 30 ring backbone atoms, including at least one, preferably 1 to 4 heteroatoms selected from the group consisting of B, N, O, S, Si, and P; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthothiophenyl, 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. In the present invention, the substituents of the substituted alkyl, the substituted cycloalkyl, the substituted cycloalkenyl, the substituted heterocycloalkyl, the substituted aryl(ene), the substituted heteroaryl(ene), and the substituted mono- or polycyclic, alicyclic or aromatic ring in Ar1, Ar2, L1, L2, and R1 to R12 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, and preferably are at least one selected from the group consisting of a (C1-C6)alkyl, a (C6-C25)aryl, a tri(C6-C12)arylsilyl, and a (C1-C6)alkyl(C6-C15)aryl.
The compound represented by formula 1 can be represented by one of the following formulas 2 and 3:
Figure PCTKR2015013231-appb-I000002
Figure PCTKR2015013231-appb-I000003
wherein
Ar1, Ar2, L1, L2, X, R1 to R4, and a to d are as defined in formula 1.
In formula 1 above, Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl, where Ar1 and Ar2 are not both phenyl; preferably each independently represent a substituted or unsubstituted (C6-C20)aryl; and more preferably each independently represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C25)aryl, a tri(C6-C12)arylsilyl, or a (C1-C6)alkyl(C6-C15)aryl.
Specifically, Ar1 and Ar2 may each independently represent one of the following structures:
Figure PCTKR2015013231-appb-I000004
Figure PCTKR2015013231-appb-I000005
Figure PCTKR2015013231-appb-I000006
Figure PCTKR2015013231-appb-I000007
L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 3- to 30-membered heteroarylene; preferably each independently represent a single bond, or a substituted or unsubstituted (C6-C12)arylene; and more preferably each independently represent a single bond, or an unsubstituted (C6-C12)arylene.
X represents O, S, CR5R6, or NR7.
R1 to R7 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, -NR8R9, or -SiR10R11R12; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; preferably each independently represent hydrogen, a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C12)aryl; and more preferably each independently represent hydrogen, an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C12)aryl.
R8 to R12 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, or a substituted or unsubstituted 3- to 30-membered heteroaryl; preferably each independently represent a substituted or unsubstituted (C6-C12)aryl; and more preferably each independently represent an unsubstituted (C6-C12)aryl.
According to one embodiment of the present invention, in formula 1 above, Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C20)aryl; L1 and L2 each independently represent a single bond, or a substituted or unsubstituted (C6-C12)arylene; X represents O, S, CR5R6, or NR7; and R1 to R7 each independently represent hydrogen, a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C12)aryl.
According to another embodiment of the present invention, in formula 1 above, Ar1 and Ar2 each independently represent (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C25)aryl, a tri(C6-C12)arylsilyl, or a (C1-C6)alkyl(C6-C15)aryl; L1 and L2 each independently represent a single bond, or an unsubstituted (C6-C12)arylene; X represents O, S, CR5R6, or NR7; and R1 to R7 each independently represent hydrogen, an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C12)aryl.
In formula 1 above, a compound where Ar1 and Ar2 are both phenyl is excluded. If the conjugation length is too short, side reactions such as cyclization occur when the compound of formula 1 becomes an exciton, and charges are not efficiently migrated.
In addition, since the three-dimensional shape changes according to how the substituents are bonded to diphenylmethyl in formula 1, it highly affects the efficiency of the device, etc. This is because when a molecule such as dibenzofuran is bonded via 3- or 4-position carbon thereof (1- or 2- position of carbazole), it will be placed at a position near to the phenyl of the substituent, and an atom having high polarity such as oxygen will be less exposed to the space compared to when the molecule is bonded via 2-position carbon thereof (3- position of carbazole). This affects the charge transportation of materials and properties of device in a preferable way. When an atom having high polarity is highly exposed to the space, it interacts with charges in the device and can operate as a disturbing factor for efficient transportation.
Meanwhile, in case of a molecule having no polar atom such as fluorene, the most ordinary form of bondage via 3-position carbon thereof is the most preferable embodiment.
The organic electroluminescent compound represented by formula 1 includes the following compounds, but is not limited thereto:
Figure PCTKR2015013231-appb-I000008
Figure PCTKR2015013231-appb-I000009
Figure PCTKR2015013231-appb-I000010
Figure PCTKR2015013231-appb-I000011
Figure PCTKR2015013231-appb-I000012
Figure PCTKR2015013231-appb-I000013
Figure PCTKR2015013231-appb-I000014
Figure PCTKR2015013231-appb-I000015
Figure PCTKR2015013231-appb-I000016
Figure PCTKR2015013231-appb-I000017
Figure PCTKR2015013231-appb-I000018
Figure PCTKR2015013231-appb-I000019
Figure PCTKR2015013231-appb-I000020
Figure PCTKR2015013231-appb-I000021
Figure PCTKR2015013231-appb-I000022
The organic electroluminescent compound of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, it can be prepared according to the following reaction scheme.
[Reaction Scheme 1]
Figure PCTKR2015013231-appb-I000023
wherein Ar1, Ar2, L1, L2, X, R1 to R4, and a to d are as defined in formula 1.
The present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
The above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
The organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes. The organic layer may comprise at least one organic electroluminescent compound of formula 1.
One of the first and second electrodes can be an anode, and the other can be a cathode. The organic layer comprises a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound of the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound of the present invention can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound of the present invention can be comprised as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more host compounds, and can further comprise one or more dopants.
When the organic electroluminescent compound of the present invention is comprised as a host material (first host material) of the light-emitting layer, another compound can be comprised as a second host material. Herein, the weight ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
The host material of a compound other than the organic electroluminescent compound of the present invention can be any of the known phosphorescent hosts. Specifically, the compound selected from the group consisting of the compounds of formulae 11 to 13 below is preferable in terms of luminous efficiency.
Figure PCTKR2015013231-appb-I000024
Figure PCTKR2015013231-appb-I000025
wherein Cz represents the following structure;
Figure PCTKR2015013231-appb-I000026
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, or -SiR25R26R27, R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 5- to 30-membered heteroarylene;
M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl;
Y1 and Y2 each independently represent -O-, -S-, -N(R31)-, or -C(R32)(R33)-, provided that Y1 and Y2 do not simultaneously exist;
R31 to R33 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl, and R32 and R33 may be the same or different;
h and i each independently represent an integer of 1 to 3;
j, k, 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 host material are as follows:
Figure PCTKR2015013231-appb-I000027
Figure PCTKR2015013231-appb-I000028
Figure PCTKR2015013231-appb-I000029
Figure PCTKR2015013231-appb-I000030
Figure PCTKR2015013231-appb-I000031
Figure PCTKR2015013231-appb-I000032
Figure PCTKR2015013231-appb-I000033
Figure PCTKR2015013231-appb-I000034
Figure PCTKR2015013231-appb-I000035
Figure PCTKR2015013231-appb-I000036
Figure PCTKR2015013231-appb-I000037
Figure PCTKR2015013231-appb-I000038
Figure PCTKR2015013231-appb-I000039
Figure PCTKR2015013231-appb-I000040
Figure PCTKR2015013231-appb-I000041
Figure PCTKR2015013231-appb-I000042
Figure PCTKR2015013231-appb-I000043
[wherein TPS represents a triphenylsilyl group]
The dopant comprised in the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant. The dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper, and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper, and platinum, and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopant is preferably selected from the group consisting of the compounds of formulae 101 to 103 below.
Figure PCTKR2015013231-appb-I000044
Figure PCTKR2015013231-appb-I000045
Figure PCTKR2015013231-appb-I000046
wherein L is selected from the following structures:
Figure PCTKR2015013231-appb-I000047
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
R101 to R109, and R111 to R123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a cyano, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (C3-C30)cycloalkyl; adjacent substituents of R106 to R109 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl; and adjacent substituents of R120 to R123 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., quinoline unsubstituted or substituted with alkyl or aryl;
R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R124 to R127 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl, and adjacent substituents of R208 to R211 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
r and s each independently represent an integer of 1 to 3; where r or s 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 compounds include the following:
Figure PCTKR2015013231-appb-I000048
Figure PCTKR2015013231-appb-I000049
Figure PCTKR2015013231-appb-I000050
Figure PCTKR2015013231-appb-I000051
Figure PCTKR2015013231-appb-I000052
Figure PCTKR2015013231-appb-I000053
Figure PCTKR2015013231-appb-I000054
Figure PCTKR2015013231-appb-I000055
Figure PCTKR2015013231-appb-I000056
Figure PCTKR2015013231-appb-I000057
Figure PCTKR2015013231-appb-I000058
Figure PCTKR2015013231-appb-I000059
Figure PCTKR2015013231-appb-I000060
Figure PCTKR2015013231-appb-I000061
Figure PCTKR2015013231-appb-I000062
Figure PCTKR2015013231-appb-I000063
Figure PCTKR2015013231-appb-I000064
Figure PCTKR2015013231-appb-I000065
Figure PCTKR2015013231-appb-I000066
Figure PCTKR2015013231-appb-I000067
Figure PCTKR2015013231-appb-I000068
Figure PCTKR2015013231-appb-I000069
Figure PCTKR2015013231-appb-I000070
Figure PCTKR2015013231-appb-I000071
Figure PCTKR2015013231-appb-I000072
In another embodiment of the present invention, a composition for preparing an organic electroluminescent device is provided. The composition comprises the compound according to the present invention as a host material or a hole transport material.
In addition, the organic electroluminescent device according to the present invention comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes. The organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for preparing the organic electroluminescent device according to the present invention.
The organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device according to the present invention, the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising said metal. The organic layer may further comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if necessary, 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 (including 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 reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Further, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
In order to form each layer of the organic electroluminescent device according to the present invention, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the organic electroluminescent compound, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound C-1
Figure PCTKR2015013231-appb-I000073
Preparation of compound 1-1
After introducing benzoyl chloride (45 mL, 376 mmol), 4-dibenzofuryl-boronic acid (40 g, 188.7 mmol), tetrakis(triphenylphosphine)palladium (6.5 g, 5.66 mmol), cesium carbonate (92 g, 283 mmol), and toluene 1 L in a reaction vessel, the mixture was stirred at 120°C for 2 hours. After the reaction is completed, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining product was then purified with column chromatography to obtain compound 1-1 (46 g, 90%).
Preparation of compound 1-2
After introducing compound 1-1 (38 g, 140 mmol) and tetrahydrofuran 500 mL in a reaction vessel, the mixture was subjected to nitrogen atmosphere and cooled to 0°C. Phenylmagnesium bromide solution 60 mL (3 M, 182 mmol) was then slowly added dropwise to the mixture. The temperature was slowly increased and the mixture was stirred under reflux for 3 hours. Ammonium chloride aqueous solution was added to the reactant solution to complete the reaction, and extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining product was then purified with column chromatography to obtain compound 1-2 (29 g, 59%).
Preparation of compound 1-3
After introducing compound 1-2 (28.5 g, 81 mmol), 4-bromotriphenylamine (53 g, 162 mmol), and methylene chloride (MC) 400 mL in a reaction vessel, the mixture was subjected to nitrogen atmosphere. Eaton’s reagent 2.5 mL was then slowly added dropwise to the mixture. After stirring the mixture at room temperature for 2 hours, ethanol and distilled water were added to the mixture to complete the reaction, and extracted with methylene chloride. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining product was then purified with column chromatography to obtain compound 1-3 (28.5 g, 54%).
Preparation of compound C-1
After introducing compound 1-3 (10 g, 15.2 mmol), 2-naphthylboronic acid (3.1 g, 18.2 mmol), tetrakis(triphenylphosphine)palladium (0.7 g, 0.61 mmol), potassium carbonate (5.2 g, 38 mmol), toluene 60 mL, and ethanol 20 mL in a reaction vessel, distilled water 20 mL was added thereto and the mixture was stirred at 120°C for 3 hours. After the reaction is completed, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining product was then purified with column chromatography to obtain compound C-1 (8.7 g, 81%).
Figure PCTKR2015013231-appb-I000074
Device Example 1: Production of an OLED device comprising the
organic electroluminescent compound according to the present invention
An OLED device was produced comprising the organic electroluminescent compound according to the present invention. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water, sequentially, and was then stored in isopropanol. Next, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-diamine (compound HI-1) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a first hole injection layer having a thickness of 80 nm on the ITO substrate. 1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile (compound HI-2) was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 3 nm on the first hole injection layer. N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine (compound HT-1) was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer. Compound C-1 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer. Thereafter, compound H-1 as below was introduced into one cell of the vacuum vapor depositing apparatus as a host, and compound D-96 was introduced into another cell as a dopant. The two materials were evaporated at different rates and were deposited in a doping amount of 2 wt% (the amount of dopant) based on the total amount of the dopant and host to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer. 2,4-bis(9,9-dimethyl-9H-fluoren-2-yl)-6-(naphthalen-2-yl)-1,3,5-triazine (compound ET-1) and lithium quinolate (compound EI-1) were then introduced into another two cells, evaporated at the rate of 1:1, and deposited to form an electron transport layer having a thickness of 35 nm on the light-emitting layer. Next, after depositing lithium quinolate (compound EI-1) as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 80 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced.
Figure PCTKR2015013231-appb-I000075
Figure PCTKR2015013231-appb-I000076
The produced OLED device showed a red emission having a luminance of 1000 cd/m2 and a current density of 3.67 mA/cm2.
Comparative Example 1: Production of an OLED device comprising
a conventional organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 1, except for depositing N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine (compound HT-1) at a thickness of 60 nm for the second hole transport layer.
The produced OLED device showed a red emission having a luminance of 1000 cd/m2 and a current density of 7.5 mA/cm2.
Compared to the conventional materials, the organic electroluminescent compound according to the present invention showed excellent luminous characteristics. In addition, the device using the organic electroluminescent compound of the present invention has excellent luminous characteristics.

Claims (8)

1. An organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2015013231-appb-I000077
wherein
Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl;
where Ar1 and Ar2 are not both phenyl;
L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 3- to 30-membered heteroarylene;
X represents O, S, CR5R6, or NR7;
R1 to R7 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, -NR8R9, or -SiR10R11R12; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
R8 to R12 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, or a substituted or unsubstituted 3- to 30-membered heteroaryl;
a represents an integer of 1 to 4, where a is an integer of 2 or more, each of R1 may be the same or different;
b represents an integer of 1 to 3, where b is an integer of 2 or more, each of R2 may be the same or different;
c and d each independently represent an integer of 1 to 5, where c or d is an integer of 2 or more, each of R3 and each of R4 may be the same or different; and
the heteroaryl(ene) and heterocycloalkyl each independently contain at least one hetero atom selected from B, N, O, S, Si, and P.
The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted alkyl, the substituted cycloalkyl, the substituted cycloalkenyl, the substituted heterocycloalkyl, the substituted aryl(ene), the substituted heteroaryl(ene), and the substituted mono- or polycyclic, alicyclic or aromatic ring in Ar1, Ar2, L1, L2, and R1 to R12 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 organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is represented by one of the following formulas 2 and 3:
Figure PCTKR2015013231-appb-I000078
Figure PCTKR2015013231-appb-I000079
wherein
Ar1, Ar2, L1, L2, X, R1 to R4, and a to d are as defined in claim 1.
The organic electroluminescent compound according to claim 1, wherein Ar1 and Ar2 each independently represent one of the following structures:
Figure PCTKR2015013231-appb-I000080
Figure PCTKR2015013231-appb-I000081
Figure PCTKR2015013231-appb-I000082
Figure PCTKR2015013231-appb-I000083
The organic electroluminescent compound according to claim 1, wherein
Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C20)aryl;
L1 and L2 each independently represent a single bond, or a substituted or unsubstituted (C6-C12)arylene;
X represents O, S, CR5R6, or NR7; and
R1 to R7 each independently represent hydrogen, a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C12)aryl.
The organic electroluminescent compound according to claim 1, wherein
Ar1 and Ar2 each independently represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C25)aryl, a tri(C6-C12)arylsilyl, or a (C1-C6)alkyl(C6-C15)aryl;
L1 and L2 each independently represent a single bond, or an unsubstituted (C6-C12)arylene;
X represents O, S, CR5R6, or NR7; and
R1 to R7 each independently represent hydrogen, an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C12)aryl.
The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
Figure PCTKR2015013231-appb-I000084
Figure PCTKR2015013231-appb-I000085
Figure PCTKR2015013231-appb-I000086
Figure PCTKR2015013231-appb-I000087
Figure PCTKR2015013231-appb-I000088
Figure PCTKR2015013231-appb-I000089
Figure PCTKR2015013231-appb-I000090
Figure PCTKR2015013231-appb-I000091
Figure PCTKR2015013231-appb-I000092
Figure PCTKR2015013231-appb-I000093
Figure PCTKR2015013231-appb-I000094
Figure PCTKR2015013231-appb-I000095
Figure PCTKR2015013231-appb-I000096
Figure PCTKR2015013231-appb-I000097
Figure PCTKR2015013231-appb-I000098
An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
PCT/KR2015/013231 2014-12-04 2015-12-04 Organic electroluminescent compound and organic electroluminescent device comprising the same Ceased WO2016089162A1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009170816A (en) * 2008-01-18 2009-07-30 Mitsui Chemicals Inc Fluorene derivative and organic electroluminescent device containing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009170816A (en) * 2008-01-18 2009-07-30 Mitsui Chemicals Inc Fluorene derivative and organic electroluminescent device containing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LEE, C.W. ET AL.: "Synthesis and photophysical properties of host materials with high triplet energy based on dibenzofuran and triphenylamine functionalities", SYNTHETIC METALS, vol. 162, 2012, pages 2059 - 2062 *

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