Patent Application
20230284515
The present invention relates to a polycyclic aromatic derivative compound and a highly efficient and long-lasting organic light-emitting device with remarkably improved luminous efficacy using the same.
An organic light-emitting device is a self-luminous device that emits light when energy is released from excitons which are formed by recombination of electrons injected from an electron injection electrode (cathode) and holes injected from a hole injection electrode (anode) in a light-emitting layer. Such an organic light-emitting device attracts a great deal of attention as a next-generation light source due to applicability to full-color flat panel light-emitting displays based on advantages such as low driving voltage, high luminance, wide viewing angle, and rapid response speed thereof.
In order for the organic light-emitting device to exhibit the characteristics, the structure of the organic layer in the organic light-emitting device should be optimized, and the material constituting each organic layer, namely, a hole injection material, a hole transport material, a light-emitting material, an electron transport material, an electron injection material, or an electron blocking material should be based on stable and efficient ingredients. However, there is a continuing need to develop organic layer structures and respective materials thereof for stable and efficient organic light-emitting devices.
In addition, recently, in addition to research on improving the characteristics of an organic light-emitting device by changing the performance of each organic layer material, technology for improving color purity and increasing luminous efficacy by optimizing the optical thickness between an anode and a cathode is considered as an important factor to improve performance. As an example of this method, a desired luminous efficacy and excellent color purity can be obtained using a capping layer for an electrode.
As such, there is a continuing need for the development of the structure of an organic light-emitting device capable of improving the luminous characteristics thereof and the development of novel materials supporting the structure.
Therefore, the present invention has been made in view of the above problems and it is one object of the present invention to provide an organic light-emitting compound that can be used in an organic layer of a device to realize a highly efficient organic light-emitting device and an organic light-emitting device including the same.
In accordance with the present invention, the above and other objects can be accomplished by the provision of a compound having an organic light-emitting compound represented by the following [Formula A] or [Formula B].
More specific structures of [Formula A] and [Formula B], definitions of Q1 to Q2, Y1 to Y6, X, and Y, and specific polycyclic aromatic compounds according to the present invention represented by [Formula A] and [Formula B] will be described later.
In accordance with another aspect of the present invention, provided is an organic light-emitting device including a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes at least one of polycyclic aromatic compounds represented by [Formula A] and [Formula B].
The polycyclic aromatic compound according to the present invention can be used for an organic layer in a device to realize a highly efficient and long-lasting organic light-emitting device.
Hereinafter, the present invention will be described in detail with reference to the annexed drawings.
The present invention is directed to a polycyclic aromatic derivative compound that is included in an organic light-emitting device, is represented by the following [Formula A] or [Formula B], and is capable of realizing a highly efficient organic light-emitting device with greatly improved lifespan,
R1 to R5 are identical to or different from each other and are each independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C5-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C5-C30 arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a nitro group, a cyano group, and a halogen group.
Also, R1 to R5 may be bonded to each other or may be each linked to an adjacent substituent to further form an alicyclic or aromatic monocyclic or polycyclic ring, and may be bonded to the Q1 to Q2 ring to further form an alicyclic or aromatic monocyclic or polycyclic ring.
In addition, the substituents of Q1 to Q2 may be bonded to the adjacent Y to further form an alicyclic or aromatic monocyclic or polycyclic ring.
Examples of the specific structure thereof can be confirmed from specific compounds according to the present invention described later.
According to an embodiment of the present invention, skeletal structures such as the following [Formula A-1] to [Formula B-1] may be formed, various polycyclic aromatic skeletal structures may be formed, and a highly efficient and long-lasting organic light-emitting device can be obtained by satisfying various organic material layers based thereon.
According to an embodiment of the present invention, all of Z's may be CR, and at least one of Z's may be N′ in order to satisfy desired conditions for various organic material layers of the organic light-emitting device.
R's may be bonded to each other or each thereof may be linked to an adjacent substituent to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atom of the formed alicyclic or aromatic monocyclic or polycyclic ring may be substituted with at least one heteroatom selected from N, S and O.
R's may be bonded to Y to further form an alicyclic or aromatic monocyclic or polycyclic ring.
X, Y, and Y1 to Y6 are as defined in [Formula A] and [Formula B].
As used herein, the term “substituted” in the definition of Q1 to Q2, R, and R1 to R9 in Formulae A and B indicates substitution with one or more substituents selected from deuterium, cyano, halogen, hydroxyl, nitro, C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 haloalkyl, C1-C24 alkenyl, C1-C24 alkynyl, C1-C24 heteroalkyl, C1-C24 heterocycloalkyl, C6-C24 aryl, C6-C24 arylalkyl, C2-C24 heteroaryl, C2-C24 heteroarylalkyl, C1-C24 alkoxy, C1-C24 alkylamino, C1-C24 arylamino, C1-C24 heteroarylamino, C1-C24 alkylsilyl, C1-C24 arylsilyl, and C1-C24 aryloxy, or a combination thereof. As used herein, the term “unsubstituted” indicates having no substituent.
In the “substituted or unsubstituted C1-C10 alkyl”, “substituted or unsubstituted C6-C30 aryl”, etc., the number of carbon atoms in the alkyl or aryl group indicates the number of carbon atoms constituting the unsubstituted alkyl or aryl moiety without considering the number of carbon atoms in the substituent(s). For example, a phenyl group substituted with a butyl group at the para-position corresponds to a C6 aryl group substituted with a C4 butyl group.
As used herein, the expression “form a ring with an adjacent substituent” means that the corresponding substituent combines with an adjacent substituent to form a substituted or unsubstituted alicyclic or aromatic ring and the term “adjacent substituent” may mean a substituent on an atom directly attached to an atom substituted with the corresponding substituent, a substituent disposed sterically closest to the corresponding substituent or another substituent on an atom substituted with the corresponding substituent. For example, two substituents substituted at the ortho position of a benzene ring or two substituents on the same carbon in an aliphatic ring may be considered “adjacent” to each other.
The alkyl groups may be straight or branched, and the numbers of carbon atoms therein are not particularly limited but are preferably 1 to 20. Specific examples of the alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl groups.
The alkenyl group is intended to include straight and branched ones and may be optionally substituted with one or more other substituents. The alkenyl group may be specifically a vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl or styrenyl group but is not limited thereto.
The alkynyl group is intended to include straight and branched ones and may be optionally substituted with one or more other substituents. The alkynyl group may be, for example, ethynyl or 2-propynyl but is not limited thereto.
The cycloalkyl group is intended to include monocyclic and polycyclic ones and may be optionally substituted with one or more other substituents. As used herein, the term “polycyclic” means that the cycloalkyl group may be directly attached or fused to one or more other cyclic groups. The other cyclic groups may be cycloalkyl groups and other examples thereof include heterocycloalkyl, aryl, and heteroaryl groups. The cycloalkyl group may be specifically a cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl or cyclooctyl group but is not limited thereto.
The heterocycloalkyl group is intended to include monocyclic and polycyclic ones interrupted by a heteroatom such as O, S, Se, N or Si and may be optionally substituted with one or more other substituents. As used herein, the term “polycyclic” means that the heterocycloalkyl group may be directly attached or fused to one or more other cyclic groups. The other cyclic groups may be heterocycloalkyl groups and other examples thereof include cycloalkyl, aryl, and heteroaryl groups.
The aryl groups may be monocyclic or polycyclic ones. Examples of the monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, and stilbenyl groups. Examples of the polycyclic aryl groups include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, tetracenyl, chrysenyl, fluorenyl, acenaphathcenyl, triphenylene, and fluoranthrene groups but the scope of the present invention is not limited thereto.
The heteroaryl groups refer to heterocyclic groups interrupted by one or more heteroatoms. Examples of the heteroaryl groups include, but are not limited to, thiophene, furan, pyrrole, imidazole, triazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, pyrimidyl, triazine, triazole, acridyl, pyridazine, pyrazinyl, quinolinyl, quinazoline, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinoline, indole, carbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, dibenzofuranyl, phenanthroline, thiazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, benzothiazolyl, and phenothiazinyl groups.
The mixed aliphatic-aromatic ring refers to a ring in which at least one aliphatic ring and at least one aromatic ring are linked or fused together and which is overall non-aromatic. The mixed aliphatic-aromatic polycyclic ring may contain one or more heteroatoms selected from N, O, P, and S other than carbon atoms (C).
The alkoxy group may be specifically a methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy or hexyloxy group but is not limited thereto.
The silyl group is intended to include alkyl-substituted silyl groups and aryl-substituted silyl groups. Specific examples of such silyl groups include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, and dimethylfurylsilyl.
The amine groups may be, for example, —NH2, alkylamine groups, and arylamine groups. The arylamine groups are aryl-substituted amine groups and the alkylamine groups are alkyl-substituted amine groups. Examples of the arylamine groups include substituted or unsubstituted monoarylamine groups, substituted or unsubstituted diarylamine groups, and substituted or unsubstituted triarylamine groups. The aryl moieties in the arylamine groups may be monocyclic or polycyclic ones. The arylamine groups may include two or more aryl moieties. In this case, the aryl moieties may be monocyclic or polycyclic ones. Alternatively, the aryl moieties may consist of a monocyclic aryl moiety and a polycyclic aryl moiety. The aryl moieties in the arylamine groups may be selected from those exemplified above.
The aryl moieties in the aryloxy group and the arylthioxy group are the same as those described above for the aryl groups. Specific examples of the aryloxy groups include, but are not limited to, phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethylphenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, 3-biphenyloxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryloxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, and 9-phenanthryloxy groups. The arylthioxy group may be, for example, a phenylthioxy, 2-methylphenylthioxy or 4-tert-butylphenylthioxy group but is not limited thereto.
The halogen group may be, for example, fluorine, chlorine, bromine or iodine.
More specifically, the polycyclic aromatic derivative compound represented by [Formula A] or [Formula B] according to the present invention may be selected from the following [Compound 1] to [Compound 117], specific substituents can be clearly identified therefrom and these compounds should not be construed as limiting the scope of [Formula A] or [Formula B] according to the present invention.
As can be seen from the specific compounds, a polycyclic aromatic structure including B, P, P═O, or the like is formed and substituents are introduced thereinto, thereby synthetizing organic light-emitting materials having intrinsic characteristics of the substituents. For example, by introducing, into the structures, substituents used for materials for a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, and the like used in the manufacture of the organic light-emitting device, organic light-emitting materials that satisfy the requirements for respective organic layers can be produced. Based thereon, highly efficient organic light-emitting devices can be realized. In addition, the compound according to the present invention can be useful as a material for various organic layers singly or in combination with other compounds, or can be used for a capping layer (CPL).
In addition, in another aspect, the present invention is directed to an organic light-emitting device including a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes at least one organic light-emitting compound represented by [Formula A] or [Formula B] according to the present invention.
That is, the organic light-emitting device according to an embodiment of the present invention may have a structure including a first electrode, a second electrode and at least one organic layer disposed therebetween, and the organic light-emitting device may be manufactured using a conventional method and materials for manufacturing devices, except that the organic light-emitting compound of [Formula A] or [Formula B] according to the present invention is used in the organic layer of the device.
The organic layer of the organic light-emitting device according to the present invention may have a single layer structure or a multilayer structure in which two or more organic layers are stacked. For example, the organic layer may have a structure including a hole injection layer, a hole transport layer, a hole blocking layer, a light-emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer, and the like. However, the structure of the organic layer is not limited thereto and may include a smaller or larger number of organic layers, and the preferred organic material layer structure of the organic light-emitting device according to the present invention will be described in more detail in Example which will be given later.
In addition, the organic light-emitting device according to an embodiment of the present invention includes a substrate, a first electrode (anode), an organic material layer, a second electrode (cathode), and a capping layer, wherein the capping layer is formed on top of the second electrode (top emission).
In the top-emission manner, the light formed in the light-emitting layer is emitted toward the cathode, and the light emitted toward the cathode passes through the capping layer (CPL) formed of the compound according to the present invention having a relatively high refractive index. At this time, the wavelength is amplified and thus luminous efficacy is increased.
Hereinafter, an embodiment of the organic light-emitting device according to the present invention will be described in more detail.
The organic light-emitting device according to the present invention includes an anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode, and if necessary, may further include a hole injection layer between the anode and the hole transport layer, may further include an electron injection layer between the electron transport layer and the cathode, may further include one or two intermediate layers, and may further include a hole blocking layer or an electron blocking layer. As described above, the organic light-emitting device may further include an organic layer having various functions, such as the capping layer described above, depending on characteristics thereof.
As a more preferred embodiment of the present invention, the organic layer interposed between the first electrode and the second electrode includes a light-emitting layer, the light-emitting layer includes a host and a dopant, and the compound according to the present invention represented by [Formula A] or [Formula B] is included as a dopant in the light-emitting layer.
The light emitting layer of the organic electroluminescent device according to the present invention includes, as a host compound, an anthracene derivative represented by Formula C:
Ar9 in Formula C is represented by Formula C-1:
The compound of Formula C employed in the organic electroluminescent device of the present invention may be specifically selected from the compounds of Formulae C1 to C48:
The organic electroluminescent device of the present invention may further include a hole transport layer and an electron blocking layer, each of which may include a compound represented by Formula D:
In Formula D, at least one of Ar31 to Ar34 is represented by Formula E:
The compound of Formula D employed in the organic electroluminescent device of the present invention may be specifically selected from the compounds of Formulae D1 to D79:
The compound of Formula D employed in the organic electroluminescent device of the present invention may be specifically selected from the compounds of Formulae D101 to D145:
The organic electroluminescent device of the present invention may further include a hole transport layer and an electron blocking layer, each of which may include a compound represented by Formula F:
The compound of Formula F employed in the organic electroluminescent device of the present invention may be specifically selected from the compounds of Formulae F1 to F33:
A specific structure of the organic electroluminescent device according to the present invention, a method for fabricating the device, and materials for the organic layers will be described below.
First, an anode material is coated on a substrate to form an anode. The substrate may be any of those used in general electroluminescent devices. The substrate is preferably an organic substrate or a transparent plastic substrate that is excellent in transparency, surface smoothness, ease of handling, and waterproofness. A highly transparent and conductive metal oxide such as indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2) or zinc oxide (ZnO) is used as the anode material.
A hole injecting material is coated on the anode by vacuum thermal evaporation or spin coating to form a hole injecting layer. Then, a hole transport material is coated on the hole injecting layer by vacuum thermal evaporation or spin coating to form a hole transport layer.
The hole injecting material is not specially limited so long as it is usually used in the art. Specific examples of such materials include 4,4′,4″-tris(2-naphthylphenyl-phenylamino)triphenylamine (2-TNATA), N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine (NPD), N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine (TPD), and N,N′-diphenyl-N,N′-bis(4-(phenyl-m-tolylamino)phenyl)biphenyl-4,4′-diamine (DNTPD).
The hole transport material is not specially limited so long as it is commonly used in the art. Examples of such materials include N,N′-bis(3-methylphenyl)-N,N′-diphenyl-(1,1-biphenyl)-4,4′-diamine (TPD) and N,N′-di(naphthalen-1-yl)-N,N′-diphenylbenzidine (α-NPD).
Subsequently, a hole auxiliary layer and a light emitting layer are sequentially laminated on the hole transport layer. A hole blocking layer may be optionally formed on the light emitting layer by vacuum thermal evaporation or spin coating. The hole blocking layer is formed as a thin film and blocks holes from entering a cathode through the organic light emitting layer. This role of the hole blocking layer prevents the lifetime and efficiency of the device from deteriorating. A material having a very low highest occupied molecular orbital (HOMO) energy level is used for the hole blocking layer. The hole blocking material is not particularly limited so long as it can transport electrons and has a higher ionization potential than the light emitting compound. Representative examples of suitable hole blocking materials include BAlq, BCP, and TPBI.
Examples of materials for the hole blocking layer include, but are not limited to, BAlq, BCP, Bphen, TPBI, NTAZ, BeBq2, OXD-7, and Liq.
An electron transport layer is deposited on the hole blocking layer by vacuum thermal evaporation or spin coating, and an electron injecting layer is formed thereon. A cathode metal is deposited on the electron injecting layer by vacuum thermal evaporation to form a cathode, completing the fabrication of the organic electroluminescent device.
For example, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In) or magnesium-silver (Mg—Ag) may be used as the metal for the formation of the cathode. The organic electroluminescent device may be of top emission type. In this case, a transmissive material such as ITO or IZO may be used to form the cathode.
A material for the electron transport layer functions to stably transport electrons injected from the cathode. The electron transport material may be any of those known in the art and examples thereof include, but are not limited to, quinoline derivatives, particularly tris(8-quinolinolate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10-olate (Bebq2), ADN, and oxadiazole derivatives such as PBD, BMD, and BND.
Each of the organic layers can be formed by a monomolecular deposition or solution process. According to the monomolecular deposition process, the material for each layer is evaporated into a thin film under heat and vacuum or reduced pressure. According to the solution process, the material for each layer is mixed with a suitable solvent, and then the mixture is formed into a thin film by a suitable method such as ink-jet printing, roll-to-roll coating, screen printing, spray coating, dip coating or spin coating.
The organic electroluminescent device of the present invention can be used in a display or lighting system selected from flat panel displays, flexible displays, monochromatic flat panel lighting systems, white flat panel lighting systems, flexible monochromatic lighting systems, and flexible white lighting systems.
Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, it will be obvious to those skilled in the art that these examples are merely provided for illustration of the present invention, and should not be construed as limiting the scope of the present invention.
25 g (103 mmol) of 2,3-dibromothiophene, 30.2 g (248 mmol) of phenylboronic acid, 42.8 g (310 mmol) of potassium carbonate, 4.8 g (4 mmol) of tetrakis(triphenylphosphine)palladium, 60 mL of water, 130 mL of toluene and 130 mL of 1,4-dioxane were stirred under reflux in a 500 mL reactor for 12 hours. After completion of the reaction, the reaction product was layer-separated and the organic layer was concentrated under reduced pressure. The residue was separated by chromatography to obtain 22.4 g of <Intermediate 1-a>. (yield 85.1%)
24 g (102 mmol) of <Intermediate 1-a> and 240 mL of chloroform were added to a 500 mL reactor, followed by stirring. The reaction product was cooled to 0° C., a dilution of 15.5 g (102 mmol) of bromine in 50 mL of chloroform was added dropwise, followed by stirring at room temperature for 4 hours. After completion of the reaction, an aqueous sodium thiosulfate solution was added thereto, followed by stirring and extraction with ethenyl acetate and H2O. The organic layer was concentrated under reduced pressure and separated by chromatography to obtain 30 g of <Intermediate 1-b>. (Yield: 88%)
4.5 g (16 mmol) of 1-bromo-2,3-dichlorobenzene, 5.8 g (16 mmol) of aniline, 0.1 g (1 mmol) of palladium acetate, 3 g (32 mmol) of sodium tert-butoxide, 0.2 g (1 mmol) of bis(diphenylphosphino)-1,1′-binaphthyl, and 45 mL of toluene were stirred under reflex in a 100 mL reactor for 24 hours. After completion of the reaction, the filtrate was concentrated and separated by chromatography to obtain 5.2 g of <Intermediate 1-c>. (yield 82%)
20 g (98 mmol) of <Intermediate 1-b>, 18.4 g (98 mmol) of <Intermediate 1-c>, 0.5 g (2 mmol) of palladium acetate, 18.9 g (196 mmol) of sodium tert-butoxide, 0.8 g (4 mmol) of tri-tert-butylphosphine, and 200 mL of toluene were stirred under reflux in a 500 mL reactor for 5 hours. After completion of the reaction, the filtrate was concentrated and separated by chromatography to obtain 22 g of <Intermediate 1-d>. (yield 75%)
18.5 g of <Intermediate 1-e> was obtained in the same manner as in Synthesis Example 1-4 except that <Intermediate 1-d> and diphenylamine were used instead of <Intermediate 1-b> and <Intermediate 1-c>. (yield 74.1%)
18.5 g (23 mmol) of <Intermediate 1-e> and 190 mL of tert-butylbenzene were added to a 300 mL reactor. 42.5 mL (115 mmol) of tert-butyllithium was added dropwise thereto at −78° C. After dropwise addition, the resulting product was stirred at 60° C. for 3 hours. Then, the pentane was removed by purging with nitrogen. 11.3 g (46 mmol) of boron tribromide was added dropwise thereto at −78° C. After dropwise addition, the mixture was stirred at room temperature for 2 hours, and 5.9 g (46 mmol) of N,N-diisopropylethylamine was added dropwise at 0° C. After dropwise addition, the mixture was stirred at 120° C. for 2 hours. After completion of the reaction, an aqueous solution of sodium acetate was added at room temperature and stirred. After extraction with ethyl acetate, the organic layer was concentrated and separated by column chromatography to obtain 3.4 g of <Compound 1>. (yield 15.7%)
MS (MALDI-TOF): m/z 578.20 [M+]
50 g (177 mmol) of 1-bromo-3-iodobenzene, 36.2 g (389 mmol) of aniline, 1.6 g (7 mmol) of palladium acetate, 51 g (530 mmol) of sodium tert-butoxide, 4.4 g (7 mmol) of bis(diphenylphosphino)-1,1′-binaphthyl, and 500 mL of toluene were stirred under reflux in a 1 L reactor for 24 hours. After completion of the reaction, the resulting product was filtered and the filtrate was concentrated and separated by chromatography to obtain 42.5 g of <Intermediate 2-a>. (yield 50%)
11 g (42 mmol) of <Intermediate 2-a>, 20 g (101 mmol) of <Intermediate 1-b>, 1 g (2 mmol) of palladium acetate, 12.2 g (127 mmol) of sodium tert-butoxide, 0.7 g (3 mmol) of tri-tert-butylphosphine, and 150 mL of toluene were stirred under reflux in a 250 mL reactor for 5 hours. After completion of the reaction, the resulting product was filtered and the filtrate was concentrated and separated by chromatography to obtain 11 g of <Intermediate 2-b>. (yield 65%)
2.7 g of <Compound 19> was obtained in the same manner as in Synthesis Example 1-6 except that <Intermediate 2-b> was used instead of <Intermediate 1-e>. (yield 14.7%)
MS (MALDI-TOF): m/z 736.22 [M+]
35.6 g of <Intermediate 3-a> was obtained in the same manner as in Synthesis Example 1-3 except that 1-bromo-2,3-dichloro-5-methylbenzene and 4-tert-butylaniline were used instead of 1-bromo-4-iodobenzene and aniline. (yield 71.2%)
60.0 g (355 mmol) of diphenylamine, 100.3 g (355 mmol) of 1-bromo-3-iodobenzene, 0.8 g (4 mmol) of palladium acetate, 2 g (4 mmol) of Xantphos, 68.2 g (709 mmol) of sodium tert-butoxide and 700 mL of toluene were stirred under reflux in a 2 L reactor for 2 hours. After completion of the reaction, the resulting product was filtered at room temperature and the filtrate was concentrated under reduced pressure and separated by chromatography to obtain 97 g of <Intermediate 3-b>. (yield 91.2%)
31 g of <Intermediate 3-c> was obtained in the same manner as in Synthesis Example 1-4 except that <Intermediate 3-a> and <Intermediate 3-b> were used instead of <Intermediate 1-c> and <Intermediate 1-b> (yield 77.7%)
31.6 g of <Intermediate 3-d> was obtained in the same manner as in Synthesis Example 1-3 except that <Intermediate 1-b> and 4-tert-butylaniline were used instead of <Intermediate 1-b> and 4-tert-butylaniline. (yield 68.2)
21 g of <Intermediate 3-e> was obtained in the same manner as in Synthesis Example 1-4 except that <Intermediate 3-c> and <Intermediate 3-d> were used instead of <Intermediate 1-c> and <Intermediate 1-b>. (yield 67.7)
2.4 of <Compound 97> was obtained in the same manner as in Synthesis Example 1-6 except that <Intermediate 3-e> was used instead of <Intermediate 1-e>. (yield 15.4%)
MS (MALDI-TOF): m/z 871.41 [M+]
ITO glass was patterned such that a light-emitting area of the ITO glass was adjusted to 2 mm×2 mm and was then washed. The ITO glass was mounted in a vacuum chamber, a base pressure was set to 1×10−7 torr, and DNTPD (700 Å) and [Formula H] (250 Å) were sequentially deposited on ITO. Then, a mixture of the host [BH1] described below and the compound of the present invention (3 wt %) was deposited to a thickness of 250 Å to form a light-emitting layer. Then, a mixture (1:1) of [Formula E-1] and [Formula E-2] was deposited thereon to a thickness of 300 Å to form an electron transport layer, [Formula E-1] was deposited thereon to a thickness of 5 Å to form an electron injection layer, and Al was deposited thereon to a thickness of 1,000 Å. As a result, an organic light-emitting device was fabricated. The luminous characteristics of the organic light-emitting device were measured at 0.4 mA.
Organic light-emitting devices were fabricated in the same manner as in Examples above, except that [BD1] to [BD3] were used instead of the compound used in Example 1. The luminous characteristics of the organic light-emitting device were measured at 0.4 mA. The structures of [BD1] to [BD3] are as follows.
The voltage, luminance, color coordinates and lifespan of the organic light-emitting devices manufactured according to Examples 1 to 10 and Comparative Examples 1 to 3 were measured and the results are shown in Table 1 below.
As can be seen from Examples 1 to 10, the organic light-emitting device containing the boron compound according to the present invention exhibits high external quantum efficiency and significantly improved lifespan, compared to organic light-emitting devices using Comparative Examples 1 to 3.
ITO glass was patterned such that a light-emitting area of the ITO glass was adjusted to 2 mm×2 mm and was then washed. The ITO glass was mounted in a vacuum chamber, a base pressure was set to 1×10−7 torr, and 2-TNATA (4,4′,4″-tris[2-naphthyl(phenyl)amino]triphenyl amine) (700 Å) and a hole transport layer (600 Å) were sequentially deposited on ITO. Then, a mixture of the host described in [Table 2] and the compound of the present invention (3 wt %) was deposited to a thickness of 200 Å to form a light-emitting layer. Then, [Formula E-2] was deposited thereon to a thickness of 300 Å to form an electron transport layer, [Formula E-1] was deposited thereon to a thickness of 10 Å to form an electron injection layer, MgAg was deposited thereon to a thickness of 120 Å and a capping layer was then deposited thereon to a thickness of 600 Å. As a result, an organic light-emitting device was fabricated. The luminous characteristics of the organic light-emitting device were measured at 0.4 mA.
Organic light-emitting devices were fabricated in the same manner as in Examples 11 to 18, except that Alq3 was used as a capping layer. The luminous characteristics of the organic light-emitting device were measured at 10 mA. The structure of [Alq3] is as follows.
As can be seen from Examples 11 to 18, the organic light-emitting device containing the compound according to the present invention, in particular, the organic light-emitting device according to the present invention exhibits high external quantum efficiency and significantly improved lifespan, compared to a device using the [Alq3] compound as a capping layer.
The polycyclic aromatic derivative of the present invention can be employed in an organic layer of an organic electroluminescent device to achieve high efficiency and long lifetime of the device. Due to these advantages, the organic electroluminescent device can find useful industrial application in various displays and lighting systems, including flat panel displays, flexible displays, monochromatic flat panel lighting systems, white flat panel lighting systems, flexible monochromatic lighting systems, and flexible white lighting systems.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0092566 | Jul 2020 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2020/095093 | 7/27/2020 | WO |
