WO2013085243A1 - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

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

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WO2013085243A1
WO2013085243A1 PCT/KR2012/010412 KR2012010412W WO2013085243A1 WO 2013085243 A1 WO2013085243 A1 WO 2013085243A1 KR 2012010412 W KR2012010412 W KR 2012010412W WO 2013085243 A1 WO2013085243 A1 WO 2013085243A1
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substituted
unsubstituted
organic electroluminescent
aryl
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Inventor
Young-Gil Kim
Young-Jun Cho
So-mi PARK
Hyuck-Joo Kwon
Kyung-Joo Lee
Bong-Ok Kim
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Priority to CN201280068756.9A priority Critical patent/CN104080882B/en
Priority to JP2014545808A priority patent/JP2015505837A/en
Priority to US14/363,301 priority patent/US20140336392A1/en
Publication of WO2013085243A1 publication Critical patent/WO2013085243A1/en
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Definitions

  • the present invention relates to novel organic electroluminescent compounds and organic electroluminescent device using the same.
  • An electroluminescent (EL) device is a self-light-emitting device which has advantages over other types of display devices in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in an organic EL device is the light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • the objective of the present invention is to provide an organic electroluminescent compound imparting high luminous efficiency and a long operating lifespan to a device, and having suitable color coordinate; and an organic electroluminescent device having high efficiency and a long lifespan, using said compound as a light-emitting material.
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted 3- to 30- membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group, provided that L 1 and L 2 are not simultaneously single bonds;
  • Y represents -O-, -S-, -CR 7 R 8 - or -NR 9 -;
  • R 1 to R 9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30- membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7- membered heterocycloalkyl group, a (C6-C30)cycloalkyl group fused with one or more aromatic rings, -NR 10 R 11 , -SR 12 , -OR 13 or -SiR 14 R 15 R 16 ;
  • R 10 to R 16 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30- membered heteroaryl group;
  • a, c, e and f each independently represent an integer of 1 to 4; where a, c, e and f are integers of 2 or more, each of R 1 , R 3 , R 5 and R 6 is the same or different;
  • b and d each independently represent an integer of 1 to 3; where b and d are integers of 2 or more, each of R 2 and R 4 is the same or different; and
  • the organic electroluminescent compounds according to the present invention have high luminous efficiency and good lifespan characteristics, and thus could provide an organic electroluminescent device having long operating lifespan.
  • the present invention makes it possible to manufacture a device free from crystallization since the organic electroluminescent compounds used in the present invention are highly efficient in transporting electrons. Further, the compounds have good layer formability and improve the current characteristics of the device. Therefore, it is possible to produce an organic electroluminescent device having lowered driving voltages and enhanced power efficiency.
  • the present invention relates to an organic electroluminescent compound represented by formula 1, above, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
  • 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 aryl(ene), heteroaryl(ene), alkyl, cycloalkyl, heterocycloalkyl, arylamino, trialkylsilyl and triarylsilyl groups in L 1 , L 2 , and R 1 to R 16 of formula 1, can be further substituted with at least one selected from the group consisting of: deuterium; a halogen; a (C1-C30)alkyl group substituted or unsubstituted with a halogen; a (C6-C30)aryl group substituted or unsubstituted with a halogen; a 3- to 30- membered heteroaryl group substituted or unsubstituted with a (C1-C30)alkyl or a (C6-C30)aryl; a (C3-C30)cycloalkyl group; a (C6-C30)cycloalkyl group fused with one or more aromatic rings; a 5- to 7- membered heterocyclo
  • R 1 , R 2 , Y, a and b are as defined in formula 1.
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted 3- to 30- membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group, provided that L 1 and L 2 are not simultaneously single bonds, preferably a single bond, a substituted or unsubstituted 5- to 20- membered heteroarylene group, or a substituted or unsubstituted (C6-C20)arylene group, more preferably a single bond; a 5- to 12- membered heteroarylene group unsubstituted or substituted with a (C6-C12)aryl group or a halo(C6-C12)aryl group; or a (C6-C10)arylene group unsubstituted or substituted with a (C1-C6)alkyl group or a 5- to 12- membered heteroaryl group.
  • Y represents -O-, -S-, -CR 7 R 8 - or -NR 9 -;
  • R 1 to R 9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30- membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7- membered heterocycloalkyl group, a (C6-C30)cycloalkyl group fused with one or more aromatic rings, -NR 10 R 11 , -SR 12 , -OR 13 or -SiR 14 R 15 R 16 , preferably hydrogen, a halogen, a substituted or unsubstituted (C1-C10)alkyl group, a substituted or unsubstituted (C6-C20)aryl group, or a substituted or un
  • R 10 to R 16 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30- membered heteroaryl group.
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted 5- to 20- membered heteroarylene group, or a substituted or unsubstituted (C6-C20)arylene group, provided that L 1 and L 2 are not simultaneously single bonds;
  • Y represents -O-, -S-, -CR 7 R 8 - or -NR 9 -;
  • R 1 to R 9 each independently represent hydrogen, a halogen, a substituted or unsubstituted (C6-C10)alkyl group, a substituted or unsubstituted (C6-C20)aryl group, or a substituted or unsubstituted 5- to 20- membered heteroaryl group.
  • L 1 and L 2 each independently represent a single bond; a 5- to 12- membered heteroarylene group unsubstituted or substituted with a (C6-C12)aryl group or a halo(C6-C12)aryl group; or a (C6-C10)arylene group unsubstituted or substituted with a (C1-C6)alkyl group or a 5- to 12- membered heteroaryl group, provided that L 1 and L 2 are not simultaneously single bonds, Y represents -O-, -S-, -CR 7 R 8 - or -NR 9 -, R 1 to R 9 each independently represent hydrogen; a halogen; an unsubstituted (C1-C6)alkyl group; a (C6-C10)aryl group unsubstituted or substituted with deuterium; or an unsubstituted 5- to 10- membered heteroaryl group.
  • L 1 and L 2 can each independently represent a single bond, a substituted or unsubstituted 3- to 30- membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group, provided that L 1 and L 2 are not simultaneously single bonds;
  • Y represents -O-, -S-, -CR 7 R 8 - or -NR 9 -;
  • R 1 to R 9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30- membered heteroaryl group; and the heteroarylene and arylene groups in L 1 and L 2 , and the alkyl, aryl and heteroaryl groups in R 1 to R 9 can be further substituted with at least one selected from the group consisting of deuterium; a
  • L 1 can represent a single bond, a phenylene, a biphenylene, a terphenylene, a fluorenylene, a triphenylenylene, a pyrenylene, a perylenylene, a fluoranthenylene, a thiophenylene, a pyrrolylene, a pyrazolylene, a thiazolylene, an oxazolylene, an oxadiazolylene, a triazinylene, a tetrazinylene, a triazolylene, a furazanylene, a pyridylene, a pyrimidylene, a quinolylene, an isoquinolylene, a quinazolylene, a benzofuranylene, a benzothiophenylene, an indolylene, a benzoimidazolylene, a benzothiazolylene, a benzoisothiazolylene,
  • the representative organic electroluminescent compounds of the present invention include the following compounds, but not limited thereto:
  • organic electroluminescent compounds of the present invention can be prepared according to the following reaction scheme.
  • L 1 , L 2 , R 1 to R 6 , Y, a, b, c, d, e and f are as defined in formula 1 above, and Hal represents a halogen.
  • the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the 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.
  • Said organic electroluminescent device comprises a first electrode, a second electrode, and at least one organic layer between said first and second electrodes.
  • Said organic layer may comprise at least one organic electroluminescent compound of formula 1 according to the present invention, or an organic electroluminescent material comprising the compound.
  • the organic layer comprises a light-emitting layer, and at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer and an electron blocking layer.
  • the organic electroluminescent compound according to the present invention can be comprised of in the light-emitting layer. Where used in the light-emitting layer, the organic electroluminescent compound according to the present invention can be comprised as a host material.
  • the light-emitting layer can further comprise at least one dopant and, if needed, another compound as a second host material in addition to the organic electroluminescent compound according to the present invention, wherein the ratio of the organic electroluminescent compound according to the present invention (a first host material) to the second host material can be in the range of 1:99 to 99:1.
  • the second host material can be from any of the known phosphorescent dopants.
  • the phosphorescent dopant selected from the group consisting of the compounds of formula 2 to 6 below is preferable in view of luminous efficiency.
  • X represents O or S
  • R 31 to R 34 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted of unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, or R 35 R 36 R 37 Si-; R 35 to R 37 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 3- to 30-membered heteroarylene group; M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group; Y 3
  • preferable examples of the second host material are as follows:
  • the dopant used in the manufacture of the organic electroluminescent device is preferably one or more phosphorescent dopants.
  • the phosphorescent dopant material applied to the electroluminescent device according to the present invention is not limited, but preferably may be selected from complex compounds of iridium, osmium, copper and platinum; more preferably 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 may be selected from compounds represented by the following formulas 7 to 9.
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group
  • R 101 to R 109 , and R 111 to R 123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, a cyano group, or a substituted or unsubstituted (C1-C30)alkoxy group
  • R 120 to R 123 are linked to an adjacent substituent to form a fused ring, e.g.
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; where R 124 to R 127 are aryl groups, adjacent substituents may be linked to each other to form a fused ring, e.g.
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), or a substituted or unsubstituted (C3-C30)cycloalkyl group; o and p each independently represent an integer of 1 to 3; where o or p is an integer of 2 or more, each of R 100 is the same or different; and n is an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • the organic layer of the organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compounds 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 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 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 of the organic electroluminescent device preferably selected from a chalcogenide layer, a metal halide layer and a metal oxide layer; may be placed on an inner surface(s) of one or both electrode(s).
  • 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 placed on a cathode surface of an electroluminescent medium layer.
  • Such a surface layer provides operation stability for the organic electroluminescent device.
  • 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 may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds; 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, dipping, 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.
  • An OLED device was produced using the 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.
  • 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine 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 50 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 C-17 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and 9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole was introduced into another cell as another host material, and the two materials were evaporated at the same rate, and was used as a host material.
  • Compound D-41 was introduced as a dopant, and the dopant was evaporated and deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • the produced OLED device showed a green emission having a luminance of 1260 cd/m 2 and a current density of 4.2 mA/cm 2 at a driving voltage of 5.1 V.
  • 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 that 4,4'-bis(carbazol-9-yl)biphenyl (CBP), instead of the compound according to the present invention, was introduced into the cell of the vacuum vapor depositing apparatus as a host material, and compound D-41 was used as a dopant; and a hole blocking layer having a thickness of 10 nm was deposited between the light-emitting layer and the electron transport layer by using aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolate (BAlq).
  • CBP 4,4'-bis(carbazol-9-yl)biphenyl
  • the produced OLED device showed a green emission having a luminance of 5015 cd/m 2 and a current density of 24.2 mA/cm 2 at a driving voltage of 7.9 V.
  • the organic electroluminescent compounds according to the present invention have superior luminous efficiency over conventional materials.
  • the organic electroluminescent devices using the compounds according to the present invention as a light-emitting host material have not only superior luminous efficiency but also can improve the power efficiency of the device and reduce overall power consumption by lowering driving voltages.

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Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device containing the same. Using the organic electroluminescent compounds of the present invention, it is possible to manufacture an OLED device with a long operating lifespan and high luminous efficiency. In addition, the compounds can improve the power efficiency of the device and reduce overall power consumption.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
The present invention relates to novel organic electroluminescent compounds and organic electroluminescent device using the same.
An electroluminescent (EL) device is a self-light-emitting device which has advantages over other types of display devices in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in an organic EL device is the light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
Until now, 4,4’-N,N’-dicarbazol-biphenyl (CBP) was the most widely known host material for phosphorescent substances in conventional technologies. Further, an organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) for a hole blocking layer is also known, and Pioneer (Japan) et al. developed a high performance organic EL device employing a derivative of BAlq as a host material.
Though these materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, 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 power efficiency is inversely proportional to voltage. An organic EL device comprising phosphorescent host materials provides a higher current efficiency (cd/A) than one comprising fluorescent materials. However, it has a higher driving voltage, and thus, there is less advantages in terms of power efficiency (lm/W). (3) Further, the operating lifespan of the organic EL device is short, and luminous efficiency still needs improvement.
International Patent Publication No. WO 2011/081423 discloses a carbazole compound substituted with a triphenylene group and a fluorene group. However, the compound requires high driving voltage, and so is not suitable for commercialization.
The objective of the present invention is to provide an organic electroluminescent compound imparting high luminous efficiency and a long operating lifespan to a device, and having suitable color coordinate; and an organic electroluminescent device having high efficiency and a long lifespan, using said compound as a light-emitting material.
The present inventors found that the objective above is achievable by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2012010412-appb-I000001
wherein
L1 and L2 each independently represent a single bond, a substituted or unsubstituted 3- to 30- membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group, provided that L1 and L2 are not simultaneously single bonds;
Y represents -O-, -S-, -CR7R8- or -NR9-;
R1 to R9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30- membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7- membered heterocycloalkyl group, a (C6-C30)cycloalkyl group fused with one or more aromatic rings, -NR10R11, -SR12, -OR13 or -SiR14R15R16;
R10 to R16 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30- membered heteroaryl group;
a, c, e and f each independently represent an integer of 1 to 4; where a, c, e and f are integers of 2 or more, each of R1, R3, R5 and R6 is the same or different;
b and d each independently represent an integer of 1 to 3; where b and d are integers of 2 or more, each of R2 and R4 is the same or different; and
the heterocycloalkyl group, the heteroarylene group and the heteroaryl group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
The organic electroluminescent compounds according to the present invention have high luminous efficiency and good lifespan characteristics, and thus could provide an organic electroluminescent device having long operating lifespan.
In addition, the present invention makes it possible to manufacture a device free from crystallization since the organic electroluminescent compounds used in the present invention are highly efficient in transporting electrons. Further, the compounds have good layer formability and improve the current characteristics of the device. Therefore, it is possible to produce an organic electroluminescent device having lowered driving voltages and enhanced power efficiency.
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 represented by formula 1, above, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
Hereinafter, The organic electroluminescent compound represented by the above formula 1 will be described in detail.
Herein, “alkyl” includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “alkenyl” includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.; “alkynyl” includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.; “cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “5- to 7-membered heterocycloalkyl” is a cycloalkyl having at least one heteroatom selected from B, N, O, S, P(=O), Si and P, preferably O, S and N, and 5 to 7 ring backbone atoms, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc.; “aryl(ene)” is a monocyclic or fused ring derived from an (C6-C30)aromatic hydrocarbon, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenyl naphthyl, naphthyl phenyl, fluorenyl, phenyl fluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenyl phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; “3- to 30-membered heteroaryl(ene)” is an aryl group having at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P, and 3 to 30 ring backbone atoms; 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 aryl(ene), heteroaryl(ene), alkyl, cycloalkyl, heterocycloalkyl, arylamino, trialkylsilyl and triarylsilyl groups in L1, L2, and R1 to R16 of formula 1, can be further substituted with at least one selected from the group consisting of: deuterium; a halogen; a (C1-C30)alkyl group substituted or unsubstituted with a halogen; a (C6-C30)aryl group substituted or unsubstituted with a halogen; a 3- to 30- membered heteroaryl group substituted or unsubstituted with a (C1-C30)alkyl or a (C6-C30)aryl; a (C3-C30)cycloalkyl group; a (C6-C30)cycloalkyl group fused with one or more aromatic rings; a 5- to 7- membered heterocycloalkyl group; RaRbRcSi-; a carbazolyl group; -NRdRe; -BRfRg; -PRhRi; -P(=O)RjRk; a (C6-C30)aryl(C1-C30)alkyl group; a (C1-C30)alkyl(C6-C30)aryl group; a (C1-C30)alkoxy group; and a (C6-C30)aryloxy group, wherein Ra to Rk each independently represent a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30- membered heteroaryl group, preferably are at least one selected from the group consisting of deuterium, a halogen, a (C1-C10)alkyl group, a (C6-C20)aryl group, a halo(C6-C20)aryl group, and a 5- to 20-membered heteroaryl group, more preferably are at least one selected from the group consisting of deuterium, a halogen, a (C1-C6)alkyl group, a (C6-C12)aryl group, a halo(C6-C12)aryl group, and a 5- to 12-membered heteroaryl group.
The moiety,
Figure PCTKR2012010412-appb-I000002
in formula 1, above, is selected from the following structures, but not limited thereto:
Figure PCTKR2012010412-appb-I000003
wherein R1, R2, Y, a and b are as defined in formula 1.
In formula 1, above, L1 and L2 each independently represent a single bond, a substituted or unsubstituted 3- to 30- membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group, provided that L1 and L2 are not simultaneously single bonds, preferably a single bond, a substituted or unsubstituted 5- to 20- membered heteroarylene group, or a substituted or unsubstituted (C6-C20)arylene group, more preferably a single bond; a 5- to 12- membered heteroarylene group unsubstituted or substituted with a (C6-C12)aryl group or a halo(C6-C12)aryl group; or a (C6-C10)arylene group unsubstituted or substituted with a (C1-C6)alkyl group or a 5- to 12- membered heteroaryl group.
Y represents -O-, -S-, -CR7R8- or -NR9-;
R1 to R9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30- membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7- membered heterocycloalkyl group, a (C6-C30)cycloalkyl group fused with one or more aromatic rings, -NR10R11, -SR12, -OR13 or -SiR14R15R16, preferably hydrogen, a halogen, a substituted or unsubstituted (C1-C10)alkyl group, a substituted or unsubstituted (C6-C20)aryl group, or a substituted or unsubstituted 5- to 20- membered heteroaryl group, more preferably hydrogen; a halogen; an unsubstituted (C1-C6)alkyl group; a (C6-C10)aryl group unsubstituted or substituted with deuterium; or an unsubstituted 5- to 10- membered heteroaryl group.
R10 to R16 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30- membered heteroaryl group.
According to one embodiment of the present invention in formula 1 above, L1 and L2 each independently represent a single bond, a substituted or unsubstituted 5- to 20- membered heteroarylene group, or a substituted or unsubstituted (C6-C20)arylene group, provided that L1 and L2 are not simultaneously single bonds; Y represents -O-, -S-, -CR7R8- or -NR9-; R1 to R9 each independently represent hydrogen, a halogen, a substituted or unsubstituted (C6-C10)alkyl group, a substituted or unsubstituted (C6-C20)aryl group, or a substituted or unsubstituted 5- to 20- membered heteroaryl group.
According to another embodiment of the present invention in formula 1 above, L1 and L2 each independently represent a single bond; a 5- to 12- membered heteroarylene group unsubstituted or substituted with a (C6-C12)aryl group or a halo(C6-C12)aryl group; or a (C6-C10)arylene group unsubstituted or substituted with a (C1-C6)alkyl group or a 5- to 12- membered heteroaryl group, provided that L1 and L2 are not simultaneously single bonds, Y represents -O-, -S-, -CR7R8- or -NR9-, R1 to R9 each independently represent hydrogen; a halogen; an unsubstituted (C1-C6)alkyl group; a (C6-C10)aryl group unsubstituted or substituted with deuterium; or an unsubstituted 5- to 10- membered heteroaryl group.
Specifically, L1 and L2 can each independently represent a single bond, a substituted or unsubstituted 3- to 30- membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group, provided that L1 and L2 are not simultaneously single bonds; Y represents -O-, -S-, -CR7R8- or -NR9-; R1 to R9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30- membered heteroaryl group; and the heteroarylene and arylene groups in L1 and L2, and the alkyl, aryl and heteroaryl groups in R1 to R9 can be further substituted with at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl group substituted or unsubstituted with a halogen; a (C6-C30)aryl group substituted or unsubstituted with a halogen; a 3- to 30- membered heteroaryl group substituted or unsubstituted with a (C1-C30)alkyl or a (C6-C30)aryl; a (C6-C30)aryl(C1-C30)alkyl group; and a (C1-C30)alkyl(C6-C30)aryl group.
More specifically, L1 can represent a single bond, a phenylene, a biphenylene, a terphenylene, a fluorenylene, a triphenylenylene, a pyrenylene, a perylenylene, a fluoranthenylene, a thiophenylene, a pyrrolylene, a pyrazolylene, a thiazolylene, an oxazolylene, an oxadiazolylene, a triazinylene, a tetrazinylene, a triazolylene, a furazanylene, a pyridylene, a pyrimidylene, a quinolylene, an isoquinolylene, a quinazolylene, a benzofuranylene, a benzothiophenylene, an indolylene, a benzoimidazolylene, a benzothiazolylene, a benzoisothiazolylene, a benzoisoxazolylene, a benzoxazolylene, a benzothiadiazolylene, a dibenzofuranylene or a dibenzothiophenylene, provided that L1 and L2 are not simultaneously single bonds; R1 to R9 each independently represent: hydrogen, deuterium, a fluorine, a methyl, an ethyl, an n-propyl, an i-propyl, an n-butyl, an i-butyl, a t-butyl, an n-pentyl, an i-pentyl, an n-hexyl, an n-heptyl, an n-octyl, a 2-ethylhexyl, an n-nonyl, a decyl, a dodecyl, a hexadecyl, a trifluoromethyl, a perfluoroethyl, a trifluoroethyl, a perfluoropropyl, a perfluorobutyl, a phenyl, a biphenyl, a fluorenyl, a fluoranthenyl, a triphenylenyl, a pyrenyl, a chrysenyl, a naphthacenyl, a perylenyl, a pyridyl, a pyrrolyl, a furanyl, a thiophenyl, an imidazolyl, a benzoimidazolyl, an indenyl, a pyrazinyl, a pyrimidyl, a pyridazinyl, a quinolyl, an isoquinolyl, a triazinyl, a benzofuranyl, a dibenzofuranyl, a benzothiophenyl, a dibenzothiophenyl, a pyrazolyl, an indolyl, a carbazolyl, a thiazolyl, an oxazolyl, a benzothiazolyl, a benzoxazolyl, a phenanthrolinyl, or an N-carbazolyl; and the substituents in L1, L2 and R1 to R9 can be further substituted with at least one selected from the group consisting of: deuterium, a chlorine, a fluorine, a methyl, an ethyl, an n-propyl, an i-propyl, an n-butyl, an i-butyl, a t-butyl, an n-pentyl, an i-pentyl, an n-hexyl, an n-heptyl, an n-octyl, a 2-ethylhexyl, an n-nonyl, a decyl, a dodecyl, a hexadecyl, a trifluoromethyl, a perfluoroethyl, a trifluoroethyl, a perfluoropropyl, a perfluorobutyl, a phenyl, a biphenyl, a fluorenyl, a 9,9-dimethylfluorenyl, a fluoranthenyl, a triphenylenyl, a fluorophenyl, a difluorophenyl, a trifluorophenyl, a tetrafluorophenyl, a pentafluorophenyl, a pyridyl, a pyrimidyl, a benzothiophenyl, an imidazolyl, a benzothiazolyl, a benzoimidazolyl, a pyrenyl, a perylenyl, a quinolyl and an isoquinolyl.
The representative organic electroluminescent compounds of the present invention include the following compounds, but not limited thereto:
Figure PCTKR2012010412-appb-I000004
Figure PCTKR2012010412-appb-I000005
Figure PCTKR2012010412-appb-I000006
Figure PCTKR2012010412-appb-I000007
Figure PCTKR2012010412-appb-I000008
Figure PCTKR2012010412-appb-I000009
Figure PCTKR2012010412-appb-I000010
Figure PCTKR2012010412-appb-I000011
Figure PCTKR2012010412-appb-I000012
Figure PCTKR2012010412-appb-I000013
Figure PCTKR2012010412-appb-I000014
The organic electroluminescent compounds of the present invention can be prepared according to the following reaction scheme.
[Reaction Scheme 1]
Figure PCTKR2012010412-appb-I000015
wherein L1, L2, R1 to R6, Y, a, b, c, d, e and f are as defined in formula 1 above, and Hal represents a halogen.
In addition, 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.
Said organic electroluminescent device comprises a first electrode, a second electrode, and at least one organic layer between said first and second electrodes. Said organic layer may comprise at least one organic electroluminescent compound of formula 1 according to the present invention, or an organic electroluminescent material comprising the compound.
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 at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer and an electron blocking layer.
The organic electroluminescent compound according to the present invention can be comprised of in the light-emitting layer. Where used in the light-emitting layer, the organic electroluminescent compound according to the present invention can be comprised as a host material.
The light-emitting layer can further comprise at least one dopant and, if needed, another compound as a second host material in addition to the organic electroluminescent compound according to the present invention, wherein the ratio of the organic electroluminescent compound according to the present invention (a first host material) to the second host material can be in the range of 1:99 to 99:1.
The second host material can be from any of the known phosphorescent dopants. Specifically, the phosphorescent dopant selected from the group consisting of the compounds of formula 2 to 6 below is preferable in view of luminous efficiency.
Figure PCTKR2012010412-appb-I000016
Figure PCTKR2012010412-appb-I000017
Figure PCTKR2012010412-appb-I000018
Figure PCTKR2012010412-appb-I000019
Figure PCTKR2012010412-appb-I000020
wherein Cz represents the following structure;
Figure PCTKR2012010412-appb-I000021
X represents O or S;
R31 to R34 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted of unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, or R35R36R37Si-; R35 to R37 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 3- to 30-membered heteroarylene group; M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group; Y3 and Y4 represent -O-, -S-, -N(R41)- or -C(R42)(R43)-, provided that Y3 and Y4 do not simultaneously exist; R41 to R43 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group, and R42 and R43 are 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 R31, each of R32, each of R33 or each of R34 is the same or different.
Specifically, preferable examples of the second host material are as follows:
Figure PCTKR2012010412-appb-I000022
Figure PCTKR2012010412-appb-I000023
Figure PCTKR2012010412-appb-I000024
Figure PCTKR2012010412-appb-I000025
Figure PCTKR2012010412-appb-I000026
Figure PCTKR2012010412-appb-I000027
Figure PCTKR2012010412-appb-I000028
Figure PCTKR2012010412-appb-I000029
Figure PCTKR2012010412-appb-I000030
Figure PCTKR2012010412-appb-I000031
Figure PCTKR2012010412-appb-I000032
Figure PCTKR2012010412-appb-I000033
Figure PCTKR2012010412-appb-I000034
Figure PCTKR2012010412-appb-I000035
Figure PCTKR2012010412-appb-I000036
Figure PCTKR2012010412-appb-I000037
According to the present invention, the dopant used in the manufacture of the organic electroluminescent device is preferably one or more phosphorescent dopants. The phosphorescent dopant material applied to the electroluminescent device according to the present invention is not limited, but preferably may be selected from complex compounds of iridium, osmium, copper and platinum; more preferably ortho-metallated complex compounds of iridium, osmium, copper and platinum; and even more preferably ortho-metallated iridium complex compounds.
According to the present invention, the dopant comprised in the organic electroluminescent device may be selected from compounds represented by the following formulas 7 to 9.
Figure PCTKR2012010412-appb-I000038
Figure PCTKR2012010412-appb-I000039
Figure PCTKR2012010412-appb-I000040
wherein L is selected from the following structures:
Figure PCTKR2012010412-appb-I000041
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; R101 to R109, and R111 to R123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, a cyano group, or a substituted or unsubstituted (C1-C30)alkoxy group; R120 to R123 are linked to an adjacent substituent 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 group, or a substituted or unsubstituted (C6-C30)aryl group; 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 group unsubstituted or substituted with halogen(s), or a substituted or unsubstituted (C3-C30)cycloalkyl group; o and p each independently represent an integer of 1 to 3; where o or p is an integer of 2 or more, each of R100 is the same or different; and n is an integer of 1 to 3.
The phosphorescent dopant materials include the following:
Figure PCTKR2012010412-appb-I000042
Figure PCTKR2012010412-appb-I000043
Figure PCTKR2012010412-appb-I000044
Figure PCTKR2012010412-appb-I000045
Figure PCTKR2012010412-appb-I000046
Figure PCTKR2012010412-appb-I000047
Figure PCTKR2012010412-appb-I000048
Figure PCTKR2012010412-appb-I000049
Figure PCTKR2012010412-appb-I000050
Figure PCTKR2012010412-appb-I000051
Figure PCTKR2012010412-appb-I000052
Figure PCTKR2012010412-appb-I000053
Figure PCTKR2012010412-appb-I000054
Figure PCTKR2012010412-appb-I000055
Figure PCTKR2012010412-appb-I000056
Figure PCTKR2012010412-appb-I000057
Figure PCTKR2012010412-appb-I000058
The organic layer of the organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compounds 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 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 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”) of the organic electroluminescent device preferably selected from a chalcogenide layer, a metal halide layer and a metal oxide layer; may be placed on an inner surface(s) of one or both electrode(s). 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 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.
Preferably, 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 may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. 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.
As for the formation of the layers 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, dipping, flow coating methods can be used.
When applying 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.
Hereinafter, the organic electroluminescent compound, the preparation method of the compound, and the luminescent properties of the device comprising the compound of the present invention will be explained in detail with reference to the following examples:
Example 1: Preparation of compound C-17
Figure PCTKR2012010412-appb-I000059
Preparation of compound 1-1
After mixing (9-phenyl-9H-carbazol-3-yl)boronic acid (36 g, 0.13 mol), 3-bromo-9H-carbazole (25.7 g, 0.11 mol), 2 M K2CO3 (125 mL), toluene (500 mL), and ethanol (125 mL), Pd(PPh3)4 (6.0 g, 0.005 mol) was added to the mixture. Then, the mixture was stirred for 5 hours at 120°C. After completing the reaction, the mixture was cooled to room temperature and distilled water (200 mL) was added, then the mixture was extracted with ethyl acetate (EA) (800 mL). Then, the organic layer was dried with anhydrous MgSO4 to remove the remaining moisture, then distillated under reduced pressure, and then separated through a column to obtain compound 1-1 (38 g, 85 %).
Preparation of compound 1-2
After mixing compound 1-1 (25.4 g, 0.062 mol), 1,3-dibromobenzene (44 g, 0.186 mol), CuI (5.9 g, 0.031 mmol), ethylene diamine (EDA) (4.1 mL, 0.062 mol), K3PO4 (40.5 g, 0.186 mol) and toluene (500 mL), the mixture was stirred for 12 hours at 120°C. After completing the reaction, the mixture was washed with distilled water and then extracted with EA. The remaining product was dried with anhydrous MgSO4 to remove the remaining moisture, then distillated under reduced pressure and then separated through a column to obtain compound 1-2 (21.5 g, 61 %).
Preparation of compound 1-3
After putting compound 1-2 (21.3 g, 37.80 mmol) in a flask, and vacuum drying the compound, nitrogen gas was filled and then tetrahydrofuran (THF) (400 mL) was added. The mixture was cooled to -78°C, then n-buLi (19.6 mL, 49.14 mmol, 2.5 M in hexane) was slowly added to the mixture at the same temperature. After strirring the mixture for 1 hour, B(i-pro)3 (6.3 mL, 56.70 mmol) was added to the mixture at the same temperature, then the mixture was stirred for 12 hours. After completing the reaction, 1 M HCl (36 mL) was added to the mixture, and after 10 minutes, distilled water was added. Then the mixture was extracted with EA. The organic layer was dried with anhydrous MgSO4 to remove the remaining moisture, then distillated under reduced pressure, and then separated through a column to obtain compound 1-3 (14.5 g, 72 %).
Preparation of compound 1-4
While slowly adding Br2 (11.2 mL, 0.219 mol) and methylene chloride (MC) (2.1 L) to triphenylene (50 g, 0.219 mol), the mixture was stirred for 12 hours under room temperature. After completing the reaction, distilled water was added, then the mixture was extracted with EA. The organic layer was dried with anhydrous MgSO4 to remove the remaining moisture, then distillated under reduced pressure, and then washed with hexane to obtain compound 1-4 (30 g, 44 %).
Preparation of compound C-17
After mixing compound 1-4 (5 g, 0.016 mol), compound 1-3 (10.3 g, 0.019 mol), Pd(PPh3)4 (940 mg, 0.81 mmol), 2 M K2CO3 (25 mL), ethanol (25 mL) and toluene (50 mL), the mixture was stirred for 5 hours at 120°C. After completing the reaction, distilled water was added, and then the mixture was extracted with EA. Then, the organic layer was dried with anhydrous MgSO4 to remove the remaining moisture, then distillated under reduced pressure, and then separated through a column to obtain compound C-17 (2.9 g, 26 %).
MS/EIMS found 710.86; calculated 710.27
Device Example 1: Production of an OLED device using the compound according to the present invention
An OLED device was produced using the 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. 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine 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 50 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 C-17 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and 9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole was introduced into another cell as another host material, and the two materials were evaporated at the same rate, and was used as a host material. Compound D-41 was introduced as a dopant, and the dopant was evaporated and deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into a cell, and evaporated to form an electron transport layer having a thickness of 40 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 green emission having a luminance of 1260 cd/m2 and a current density of 4.2 mA/cm2 at a driving voltage of 5.1 V.
Comparative Example 1: Production of an OLED device using conventional
electroluminescent compounds
An OLED device was produced in the same manner as in Device Example 1, except that 4,4'-bis(carbazol-9-yl)biphenyl (CBP), instead of the compound according to the present invention, was introduced into the cell of the vacuum vapor depositing apparatus as a host material, and compound D-41 was used as a dopant; and a hole blocking layer having a thickness of 10 nm was deposited between the light-emitting layer and the electron transport layer by using aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolate (BAlq).
The produced OLED device showed a green emission having a luminance of 5015 cd/m2 and a current density of 24.2 mA/cm2 at a driving voltage of 7.9 V.
It is verified that the organic electroluminescent compounds according to the present invention have superior luminous efficiency over conventional materials. In addition, the organic electroluminescent devices using the compounds according to the present invention as a light-emitting host material have not only superior luminous efficiency but also can improve the power efficiency of the device and reduce overall power consumption by lowering driving voltages.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2012010412-appb-I000060
    wherein
    L1 and L2 each independently represent a single bond, a substituted or unsubstituted 3- to 30- membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group, provided that L1 and L2 are not simultaneously single bonds;
    Y represents -O-, -S-, -CR7R8- or -NR9-;
    R1 to R9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30- membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7- membered heterocycloalkyl group, a (C6-C30)cycloalkyl group fused with one or more aromatic rings, -NR10R11, -SR12, -OR13 or -SiR14R15R16;
    R10 to R16 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30- membered heteroaryl group;
    a, c, e and f each independently represent an integer of 1 to 4; where a, c, e and f are integers of 2 or more, each of R1, R3, R5 and R6 is the same or different;
    b and d each independently represent an integer of 1 to 3; where b and d are integers of 2 or more, each of R2 and R4 is the same or different; and
    the heterocycloalkyl group, the heteroarylene group and the heteroaryl group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound according to claim 1, wherein the aryl(ene), heteroaryl(ene), alkyl, cycloalkyl and heterocycloalkyl groups in L1, L2, and R1 to R16 can be further substituted with at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl group substituted or unsubstituted with a halogen; a (C6-C30)aryl group substituted or unsubstituted with a halogen; a 3- to 30- membered heteroaryl group substituted or unsubstituted with a (C1-C30)alkyl or a (C6-C30)aryl; a (C3-C30)cycloalkyl group; a (C6-C30)cycloalkyl group fused with one or more aromatic rings; a 5- to 7- membered heterocycloalkyl group; RaRbRcSi-; a carbazolyl group; -NRdRe; -BRfRg; -PRhRi; -P(=O)RjRk; a (C6-C30)aryl(C1-C30)alkyl group; a (C1-C30)alkyl(C6-C30)aryl group; a (C1-C30)alkoxy group; and a (C6-C30)aryloxy group, wherein Ra to Rk each independently represent a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30- membered heteroaryl group.
  3. The organic electroluminescent compound according to claim 1, wherein the moiety,
    Figure PCTKR2012010412-appb-I000061
    in formula 1 is selected from the following structures:
    Figure PCTKR2012010412-appb-I000062
    wherein R1, R2, Y, a and b are as defined in claim 1.
  4. The organic electroluminescent compound according to claim 1, wherein
    L1 and L2 each independently represent a single bond, a substituted or unsubstituted 3- to 30- membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group, provided that L1 and L2 are not simultaneously single bonds;
    Y represents -O-, -S-, -CR7R8- or -NR9-;
    R1 to R9 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30- membered heteroaryl group; and
    the heteroarylene and arylene groups in L1 and L2, and the alkyl, aryl and heteroaryl groups in R1 to R9 can be further substituted with at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl group substituted or unsubstituted with a halogen; a (C6-C30)aryl group substituted or unsubstituted with a halogen; a 3- to 30- membered heteroaryl group substituted or unsubstituted with a (C1-C30)alkyl or a (C6-C30)aryl; a (C6-C30)aryl(C1-C30)alkyl group; and a (C1-C30)alkyl(C6-C30)aryl group.
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2012010412-appb-I000063
    Figure PCTKR2012010412-appb-I000064
    Figure PCTKR2012010412-appb-I000065
    Figure PCTKR2012010412-appb-I000066
    Figure PCTKR2012010412-appb-I000067
    Figure PCTKR2012010412-appb-I000068
    Figure PCTKR2012010412-appb-I000069
    Figure PCTKR2012010412-appb-I000070
    Figure PCTKR2012010412-appb-I000071
    Figure PCTKR2012010412-appb-I000072
    Figure PCTKR2012010412-appb-I000073
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
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