KR101555155B1 - Novel spyrobifluorene type organic compounds and an organic electroluminescent device comprising the same - Google Patents
Novel spyrobifluorene type organic compounds and an organic electroluminescent device comprising the same Download PDFInfo
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Abstract
Description
The present invention relates to a novel spirobifluorene type organic compound used in an organic electroluminescence device and an organic electroluminescence device including the organic compound.
Bernanose, who was studying in France in the 1950s, discovered electrical properties of special organic materials. In 1963, M. Pope of the University of New York succeeded in emitting light by applying a voltage of 400V or more to a tens of microns thick anthracene A study on the organic electroluminescent device has been proposed in 1987 by Tang, which is a multilayer organic electroluminescent device divided into a hole layer and a functional layer of a light emitting layer. Then, in order to make an organic electroluminescent device such as a high efficiency, a long life, a low driving voltage, a fast response speed and a wide viewing angle, it has developed into a form in which each characteristic organic layer in the device is introduced. .
In general, the simplest structure of an organic electroluminescent device is composed of a light emitting layer and a pair of opposite electrodes sandwiching the layer. That is, in the organic electroluminescent device, when an electric field is applied between the electrodes, electrons are injected from the cathode, holes are injected from the anode, and they are recombined in the light emitting layer to emit light.
A more detailed structure of the organic electroluminescent device includes a substrate, an anode, a hole injecting layer for receiving holes in the anode, a hole transporting layer for transporting holes, an electron blocking layer for blocking electrons from entering from the light emitting layer to the hole transporting layer, A hole blocking layer for blocking the entrance of holes from the light emitting layer into the electron transporting layer, an electron transporting layer for receiving electrons from the cathode to transport electrons to the light emitting layer, an electron injection layer for receiving electrons from the cathode, and a cathode. In some cases, a light emitting layer may be formed by doping a small amount of a fluorescent or phosphorescent dye to an electron transporting layer or a hole transporting layer without a separate light emitting layer. When a polymer is used, generally one polymer acts as a hole transporting layer, a light emitting layer and an electron transporting layer Can be performed simultaneously. The organic thin film layers between the two electrodes are formed by a vacuum deposition method, a spin coating method, an inkjet printing method, a laser thermal transfer method, or the like. The reason for fabricating the organic electroluminescent device as a multilayer thin film structure is to stabilize the interface between the electrode and the organic material, and in the case of the organic material, the difference in the movement speed of holes and electrons is large. Therefore, by using a proper hole transporting layer and an electron transporting layer, And electrons are effectively transferred to the light-emitting layer so that the densities of the holes and electrons are balanced, thereby improving the luminous efficiency.
The driving principle of the organic electroluminescent device is as follows. When a voltage is applied between the anode and the cathode, the holes injected from the anode are transferred to the light emitting layer via the hole injecting layer and the hole transporting layer. On the other hand, electrons are injected from the cathode to the light emitting layer via the electron injection layer and the electron transport layer, and carriers are recombined in the light emitting layer region to generate an exiton. This exciton is changed from the excited state to the ground state, whereby the fluorescent molecules of the light emitting layer emit light, whereby an image is formed. In this case, the excitation state is referred to as " emission " when the excited state falls to the ground state through the singlet excitation state, and " phosphorescence " In the case of fluorescence, the probability of singlet excited state is 25% (triplet state 75%) and there is a limit of luminous efficiency. However, when phosphorescence is used, 75% of triplet state and 25% of singlet excitation state are used for light emission Theoretically, it is possible to raise the internal quantum efficiency to 100%.
The most problematic of such an organic electroluminescent device is its lifetime and efficiency. However, as the display becomes larger, efficiency and life time problems must be solved. The lifetime of the stacked organic electroluminescent device is related to the stability of the thin film and the material. For example, when the thermal stability of the material deteriorates, crystallization of the material occurs at a high temperature or at a driving temperature, thereby shortening the lifetime of the device. As a representative example, in the case of the dinaphthylanthracene compound, the crystallization is easily caused by increasing the temperature of the device because of the molecular structure of left and right and up and down symmetry. In recent years, thin film stability is improved by introducing a spiro structure as a means for preventing such crystallization. For example, U.S. Pat. No. 5,840,217 discloses derivatives of spirobifluorene, and U.S. Patent Nos. 5621131 and 5763636 disclose polymers comprising spiro compounds as repeating units. However, the known spiromolecules have excellent heat resistance, but have a disadvantage in that they can not exhibit high driving voltage or high efficiency of light emission. Particularly, in the case of a spiromolecule polymer, impurities or unreacted residues remain at the terminals, It is difficult to form a film by the spin-coating method or the ink-jet method.
In an organic electroluminescent device, an electron blocking layer (EBL) is formed between the light emitting layer and the hole transporting layer to prevent electrons from being injected into the hole transporting layer without bonding in the light emitting layer and to improve the probability of recombination of electrons and holes by enclosing electrons in the light emitting layer. ) Can be installed.
When the hole transport layer transmits holes well and the electron blocking layer (EBL) performs the functions as described above, the driving voltage of the device can be lowered, the luminous efficiency and brightness can be increased, and the luminous efficiency of the organic electroluminescent device The life span can be extended.
However, development of a stable and efficient compound as a material capable of forming a hole transport layer (HTL) or an electron blocking layer (EBL) has not been sufficiently developed so far.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide an organic electroluminescent device which can be applied to a hole injection layer, a hole transport layer, It is an object of the present invention to provide a novel organic compound capable of lowering the driving voltage and improving the luminous efficiency, luminance, thermal stability, color purity, and device life.
It is another object of the present invention to provide a hole injecting layer, a hole transporting layer, an electron blocking layer or a material for forming a light emitting layer containing the organic compound.
It is another object of the present invention to provide an organic electroluminescent device using the organic compound.
The present invention provides novel organic compounds represented by the following general formula
[ Formula 1 ]
In the above formula
R1 is substituted with one or more selected from hydrogen, alkoxy, halogen, CN, CF 3 and Si (CH 3) group consisting of 3 groups of C1 ~ C10 linear or branched alkyl, C3 ~ C12 cycloalkyl, C1 ~ C10 of Or an unsubstituted phenyl, pyridinyl, pyrimidinyl, or triazinyl group;
Each of R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8 and R 9 is independently selected from the group consisting of hydrogen, straight or branched chain C 1 to C 10 alkyl, C 3 to C 12 cycloalkyl, C 1 to C 10 alkoxy, 3 or Si (CH 3 ) 3 group,
Straight-chain or branched C1 ~ C10 alkyl, substituted or unsubstituted by one or more selected from alkoxy, halogen, CN, CF 3 or the group consisting of Si (CH 3) 3 groups of C3 ~ C12 cycloalkyl, C1 ~ C10 Phenyl, pyridinyl, pyrimidinyl, or triazinyl group.
The present invention also provides a hole injecting layer, a hole transporting layer, an electron blocking layer, or a material for forming a light emitting layer containing the organic compound represented by the above formula (1).
The organic electroluminescent device according to the present invention is an organic electroluminescent device in which one or more organic thin film layers including at least a light emitting layer are laminated between a cathode and an anode and in which at least one layer of the organic thin film layers is an organic An organic electroluminescent device characterized by containing a compound singly or in combination of two or more.
The organic compound according to the present invention can be applied to an organic light emitting device as a hole injecting layer material, a hole transporting layer material, an electron blocking layer material or a light emitting layer material. When applied to an organic light emitting device, Thereby improving thermal stability, color purity, and device life.
In addition, the organic electroluminescent device manufactured using the organic compound of the present invention has high efficiency and long life characteristics.
The present invention relates to novel organic compounds represented by the general formula
[ Formula 1 ]
In the above formula
R1 is substituted with one or more selected from hydrogen, alkoxy, halogen, CN, CF 3 and Si (CH 3) group consisting of 3 groups of C1 ~ C10 linear or branched alkyl, C3 ~ C12 cycloalkyl, C1 ~ C10 of Or an unsubstituted phenyl, pyridinyl, pyrimidinyl, or triazinyl group;
Each of R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8 and R 9 is independently selected from the group consisting of hydrogen, straight or branched chain C 1 to C 10 alkyl, C 3 to C 12 cycloalkyl, C 1 to C 10 alkoxy, 3 or Si (CH 3 ) 3 group,
Straight-chain or branched C1 ~ C10 alkyl, substituted or unsubstituted by one or more selected from alkoxy, halogen, CN, CF 3 or the group consisting of Si (CH 3) 3 groups of C3 ~ C12 cycloalkyl, C1 ~ C10 Phenyl, pyridinyl, pyrimidinyl, or triazinyl group.
In Formula 1, more preferably,
R1 is a phenyl, pyridinyl, pyrimidinyl, or triazinyl group substituted or unsubstituted with a C1-C10 linear or branched alkyl group;
And R < 9 > are each independently hydrogen or a linear or branched alkyl group having from 1 to 10 carbon atoms, or R <
A phenyl, pyridinyl, pyrimidinyl, or triazinyl group substituted or unsubstituted with a C1 to C10 linear or branched alkyl group.
In the above formula (1), still more preferably,
R1 is a phenyl group substituted or unsubstituted with a C1-C4 linear or branched alkyl group;
R2, R3, R4, R5, R6, R7, R8, and R9 are each independently hydrogen, a C1 to C4 linear or branched alkyl group, or a phenyl group.
Specifically, the organic compound may be any one of the following compounds 1 to 25:
The organic compounds of the present invention can be used as a hole injecting layer material, a hole transporting layer material, an electron blocking layer material, or a light emitting layer material in an organic electroluminescent device material, and more preferably, an electron blocking layer material.
The present invention also relates to a hole injecting layer, a hole transporting layer, an electron blocking layer, or a material for forming a light emitting layer, which comprises at least one selected from the compounds represented by the above formula (1).
The hole injecting layer, the hole transporting layer, the electron blocking layer or the material for forming the light emitting layer are usually added when the organic compound is prepared in a form necessary for forming the hole injecting layer, the hole transporting layer, the electron blocking layer or the light emitting layer Materials, such as solvents, and the like.
Further, the present invention is an organic electroluminescent device in which one or more organic thin film layers including at least a light emitting layer are laminated between a cathode and an anode, wherein at least one layer of the organic thin film layer contains an organic compound of the formula Type or a combination of two or more kinds of organic electroluminescent devices.
In the organic electroluminescent device, the organic compound may include at least one of a hole injecting layer material, a hole transporting layer material, an electron blocking layer material, and a light emitting layer material.
The organic electroluminescent device
A hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode may be stacked. If necessary, an electron blocking layer, a hole blocking layer, and the like may be further stacked.
The organic thin film layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and the organic compound of the present invention may be included in the hole transport layer.
The organic thin film layer includes a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron blocking layer, and an electron injecting layer. When the organic compound of the present invention is contained in at least one of the hole transporting layer and the electron blocking layer .
Hereinafter, the organic electroluminescent device of the present invention will be described by way of example. However, the following examples do not limit the organic electroluminescent device of the present invention.
The organic electroluminescent device of the present invention may have a structure in which an anode (a hole injecting electrode), a hole injecting layer (HIL), a hole transporting layer (HTL), a light emitting layer (EML), and a cathode (electron injecting electrode) Preferably, an electron blocking layer (EBL) is provided between the anode and the light emitting layer, and an electron transport layer (ETL) and an electron injection layer (EIL) are provided between the cathode and the light emitting layer. Further, a hole blocking layer (HBL) may be further included between the cathode and the light emitting layer.
In the method of manufacturing an organic electroluminescent device according to the present invention, a cathode material is coated on the surface of a substrate by a conventional method to form a cathode. At this time, the substrate to be used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness. As the material for the positive electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity may be used.
Next, a hole injection layer (HIL) material is formed on the surface of the anode by vacuum thermal deposition or spin coating using a conventional method. Examples of the hole injection layer material include the organic compound of the present invention, copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine (m-MTDATA) 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine (TCTA) which is a starburst type amine, 4,4' Triphenylamine (2-TNATA), or IDE406 available from Idemitsu, for example, can be exemplified.
A hole transport layer (HTL) material is vacuum-deposited or spin coated on the surface of the hole injection layer by a conventional method to form a hole transport layer. As the hole transport layer material, organic compound of the present invention, bis (N- (1-naphthyl-n-phenyl)) benzidine (? -NPD), N, N'- (NPB) or N, N'-biphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD) For example.
A light emitting layer (EML) material is formed on the surface of the hole transport layer by vacuum thermal deposition or spin coating using a conventional method. Among the light emitting layer materials used, a single luminescent material or a luminescent host material may be an organic compound of the present invention, tris (8-hydroxyquinolinolato) aluminum (Alq3) or the like in the case of green, Balq 8-hydroxyquinoline beryllium salts), DPVBi (4,4'-bis (2,2-biphenylethenyl) -1,1'-biphenyl) series, Spiro materials, Spiro- DPVBi (2, 2-biphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazolyl) -phenol lithium salt), bis (biphenylvinyl) benzene , Aluminum-quinoline metal complexes, metal complexes of imidazole, thiazole and oxazole, and the like can be used. The organic compound of the present invention may be used as a phosphorescent red host material.
Among the light emitting layer materials, IDE102 and IDE105 available from Idemitsu as phosphorescent dopants and tris (2-phenylpyridine) iridium (III) (Ir (ppy ) 3), iridium (III) bis [(4,6-difluorophenyl) pyridinate-N, C-2 '] picolinate (FIrpic) (Chihaya Adachi et al., Appl. Phys Platy (II) octaethylporphyrin (PtOEP), TBE002 (Cobion), etc. may be used.
An electron blocking layer may be formed by vacuum thermal evaporation or spin coating an electron blocking layer (EBL) material on the surface of the hole transport layer by a conventional method. As the electron blocking layer material, the organic compound of the present invention may be used, and compounds known in the art may be used.
An electron transport layer (ETL) material is formed on the surface of the light emitting layer by vacuum thermal deposition or spin coating using a conventional method. In this case, the electron transporting material to be used is not particularly limited, and tris (8-hydroxyquinolinolato) aluminum (Alq3) can be preferably used.
Alternatively, by further forming a hole blocking layer (HBL) between the light emitting layer and the electron transporting layer and using a phosphorescent dopant together with the light emitting layer, it is possible to prevent the phenomenon that the triplet excitons or holes are diffused into the electron transporting layer.
The hole blocking layer can be formed by vacuum thermal evaporation and spin coating using a hole blocking layer material in a conventional manner. The hole blocking layer material is not particularly limited, Hydroxyquinolinolato) lithium (Liq), bis (8-hydroxy-2-methylquinolinonato) -aluminum biphenoxide (BAlq), bathocuproine (BCP) Can be used.
An electron injection layer (EIL) material is formed on the surface of the electron transport layer by vacuum thermal deposition or spin coating using a conventional method. At this time, materials such as LiF, Liq, Li2O, BaO, NaCl, and CsF can be used as the electron injection layer material used.
A negative electrode is formed on the surface of the electron injecting layer by vacuum thermal deposition using a conventional method.
At this time, as the negative electrode material to be used, lithium, aluminum, aluminum-lithium, calcium, magnesium, (Mg-Ag) or the like may be used. In the case of a top emission organic electroluminescent device, indium tin oxide (ITO) or indium zinc oxide (IZO) may be used to form a transparent cathode which can transmit light.
Hereinafter, a method of synthesizing the above compounds will be described with reference to representative examples. However, the method of synthesizing the compounds of the present invention is not limited to the following exemplified methods, and the compounds of the present invention can be produced by the methods exemplified below and by methods known in the art.
Synthesis of intermediates A and B
[Reaction Scheme 1]
1 mol of 2-iodobiphenyl was dissolved in THF, and n-BuLi was added dropwise at -78 ° C. After stirring for 1 hour at -78 ° C, 1 mol of 2-bromo-9H-fluoren-9-one dissolved in THF was slowly added dropwise and the temperature was raised to room temperature to complete the reaction. The reaction mixture was extracted with CH 2 Cl 2 and 1N HCl, Dried over anhydrous MgSO 4 , concentrated, and then subjected to column chromatography and recrystallization to obtain Intermediate A (yield: 78%).
The intermediate A was dissolved in acetic acid, concentrated hydrochloric acid was added, and the reaction was completed by refluxing for 1 hour. After extracting with ether and water, the organic layer was separated by Sat? And washed with NaHCO 3 . The organic layer was dried over MgSO 4 and then subjected to column chromatography and recrystallization to obtain Intermediate B (yield: 85%).
Intermediate A MS (FAB): 413 (M < + & gt ; ) [
Intermediate B MS (FAB): 395 (M <+> ),
Synthesis of intermediate C
[Reaction Scheme 2]
Intermediate B was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 < 0 > C, n-BuLi was slowly added dropwise and the reaction was stirred at 0 < 0 > C for 1 hour. Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.
Water in the organic layer was removed with anhydrous MgSO 4 , filtered under reduced pressure, and the organic solvent was concentrated. The resulting compound was subjected to column chromatography and recrystallization to obtain the desired intermediate C (yield: 81%).
Intermediate C MS (FAB): 360 (M <+> )
Synthesis of intermediate D
[Reaction Scheme 3]
1 mol of Intermediate C and 1-bromo-3-iodobenzene were added, respectively, and Pd (PPh 3 ) 4 , 2M K 2 CO 3 and THF were added. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and water. The organic layer was dried over anhydrous MgSO 4, and the organic solvent was concentrated. The resulting compound was subjected to column chromatography and recrystallization to obtain the desired intermediate D : 77%).
Intermediate D MS (FAB): 471 (M < + & gt ; ) [
Synthesis of intermediate E
[Reaction Scheme 4]
1 mol of Intermediate C and 1-bromo-4-iodobenzene were added, respectively, and Pd (PPh 3 ) 4 , 2M K 2 CO 3 and THF were added. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and water. The organic layer was dried over anhydrous MgSO 4, and the organic solvent was concentrated. The resulting compound was subjected to column chromatography and recrystallization to obtain the desired intermediate E : 77%).
Intermediate E MS (FAB): 471 (M < + & gt ; ) [
Synthesis of Intermediates F and G
[Reaction Scheme 5]
1 mol of 2-iodobiphenyl was dissolved in THF, and n-BuLi was added dropwise at -78 ° C. After stirring for 1 hour at -78 ° C, 1 mol of 4-bromo-9H-fluoren-9-one dissolved in THF was slowly added dropwise and the temperature was raised to room temperature. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and 1N HCl, Dried over anhydrous MgSO 4 , concentrated, and then subjected to column chromatography and recrystallization to obtain Intermediate F (yield: 73%).
Intermediate F was dissolved in acetic acid, concentrated hydrochloric acid was added, and the reaction was completed by refluxing for 1 hour. After extracting with ether and water, the organic layer was separated by Sat? And washed with NaHCO 3 . The organic layer was dried over MgSO 4 and then subjected to column chromatography and recrystallization to obtain Intermediate G (yield: 84%).
Intermediate F MS (FAB): 413 (M <+> ) <
Intermediate G MS (FAB): 395 (M <+> )
Synthesis of Intermediate H
[Reaction Scheme 6]
Intermediate G was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.
The water in the organic layer was removed with anhydrous MgSO 4 , filtered under reduced pressure, and the organic solvent was concentrated. The resulting compound was subjected to column chromatography and recrystallization to obtain the desired intermediate H (yield: 81%).
Intermediate H MS (FAB): 360 (M <+> )
Synthesis of Intermediate I
[Reaction Scheme 7]
1 mol of Intermediate H and 1-bromo-3-iodobenzene were added, and Pd (PPh 3 ) 4 , 2M K 2 CO 3 and THF were added, respectively, and refluxed for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and water. The organic layer was dried over anhydrous MgSO 4, and the organic solvent was concentrated. The resulting compound was subjected to column chromatography and recrystallization to obtain the desired intermediate I : 77%).
Intermediate I MS (FAB): 471 (M < + & gt ; ) [
Synthesis of intermediate J
[Reaction Scheme 8]
Intermediate H and 1-bromo-4-iodobenzene were injected into the reactor, respectively, and Pd (PPh 3 ) 4 , 2M K 2 CO 3 and THF were added. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and water. The organic layer was dried over anhydrous MgSO 4, and the organic solvent was concentrated. The resulting compound was subjected to column chromatography and recrystallization to obtain the desired intermediate J : 77%).
Intermediate J MS (FAB): 471 (M < + & gt ; ) [
Synthesis of Intermediates K and L
[Reaction Scheme 9]
1 mol of 2-iodobiphenyl was dissolved in THF, and n-BuLi was added dropwise at -78 ° C. After stirring for 1 hour, 1 mol of 2,7-dibromo-9H-fluoren-9-one was dissolved in THF and added dropwise. The mixture was heated to room temperature and stirred for 1 hour. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and 1N HCl. The organic layer was dried over MgSO 4 and then purified by column chromatography and recrystallization to obtain Intermediate K (71% yield). Intermediate K was dissolved in acetic acid, concentrated hydrochloric acid was added, and the reaction was completed by refluxing for 1 hour. After extracting with ether and water, the organic layer was separated by Sat? And washed with NaHCO 3 . The organic layer was dried over MgSO 4 and then subjected to column chromatography and recrystallization to obtain Intermediate L (yield: 82%).
Intermediate K MS (FAB): 492 (M <+> )
Intermediate L MS (FAB): 474 (M <+> ) <
Synthesis of intermediate M
[Reaction Scheme 10]
Each injection by 1mol Intermediate L and phenylboronic acid, and insert the Pd (PPh 3) 4, 2M K 2 CO 3, THF , respectively, and then the mixture was refluxed for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and water. The organic layer was dried over anhydrous MgSO 4 and then subjected to column chromatography and recrystallization to obtain the desired intermediate M (yield: 65% .
Intermediate M MS (FAB): 471 (M < + & gt ; ) [
Synthesis of Intermediate N
[Reaction Scheme 11]
Phenylboronic acid and 4-bromoaniline were injected at 1 mol each, Pd (PPh 3 ) 4 , 2M K 2 CO 3, and THF were added, respectively, and refluxed for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and water. The organic layer was dried over anhydrous MgSO 4 and concentrated. The resulting product was subjected to column chromatography and recrystallization to obtain the desired intermediate N (Yield: 77 %).
Intermediate N MS (FAB): 169 (M <+> ) <
Synthesis of Intermediate O
[Reaction Scheme 12]
After implanting N 1.2mol intermediate and intermediate D and 1mol dissolved Pd 2 dba 3, t-Bu 3 P and t-BuONa in THF solvent, and stirred for 2 hours at 110 ℃. After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with toluene and water. The organic layer was dried over anhydrous MgSO 4 and concentrated. The resulting compound was subjected to column chromatography and recrystallization to obtain the desired intermediate O (yield: 81%).
Intermediate O MS (FAB): 559 (M < + & gt ; ).
Synthesis of intermediate P
[Reaction Scheme 13]
After implanting N 1.2mol intermediate and intermediate E 1mol and dissolved Pd 2 dba 3, t-Bu 3 P and t-BuONa in THF solvent, and stirred for 2 hours at 110 ℃. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with toluene and water. The organic layer was dried over anhydrous MgSO 4 and concentrated. The resulting compound was subjected to column chromatography and recrystallization to obtain the desired intermediate P (yield: 81%).
Intermediate P MS (FAB): 559 (M <+> )
Preparation of compound [5]
[Reaction Scheme 14]
Pd 2 dba 3 , t-Bu 3 P, t-BuONa, and toluene were added to each of the intermediate B and the intermediate P, followed by stirring at 110 ° C for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and water, and a small amount of water in the organic layer was removed with anhydrous MgSO 4. After filtration under reduced pressure, the organic solvent was concentrated. And the desired compound 5 was obtained (yield: 78%).
1 H NMR (CDCl3, 300Hz) : δ (ppm) = 7.90-7.87 (d, 1H), 7.87-7.82 (d, 5H), 7.80-7.70 (d, 1H), 7.65-6.90 (m, 30H), 6.80-6.60 (m, 6H)
MS (FAB): 874 (M < + & gt ; ).
Preparation of compound [12]
[Reaction Scheme 15]
Pd 2 dba 3 , t-Bu 3 P, t-BuONa, and toluene were added, respectively, and the mixture was stirred at 110 ° C for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with CH 2 Cl 2 and water. A small amount of water in the organic layer was removed with anhydrous MgSO 4 , filtered under reduced pressure, the organic solvent was concentrated, Chromatography and recrystallization gave the desired compound 12 (Yield: 74%).
1 H NMR (CDCl3, 300Hz) : δ (ppm) = 7.90-7.87 (d, 1H), 7.87-7.82 (d, 5H), 7.77-7.72 (d, 1H), 7.65-6.90 (m, 29H), 6.80-6.60 (m, 7H)
MS (FAB): 874 (M < + & gt ; ).
Preparation of compound [22]
[Reaction Scheme 16]
Pd 2 dba 3 , t-Bu 3 P, t-BuONa and toluene were added to each of the intermediate M and the intermediate O, followed by stirring at 110 ° C for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with CH 2 Cl 2 and water. A small amount of water in the organic layer was removed with anhydrous MgSO 4 , filtered under reduced pressure, the organic solvent was concentrated, Chromatography and recrystallization gave the desired compound 22 (Yield: 77%).
1 H NMR (CDCl3, 300Hz) : δ (ppm) = 7.90-7.87 (d, 1H), 7.87-7.82 (d, 5H), 7.80-7.70 (d, 1H), 7.65-6.90 (m, 33H), 6.80-6.60 (m, 7H)
MS (FAB): 950 (M < + & gt ; ).
Using the method of Scheme 1-16, the compounds 1 to 25 of the formula 1 were prepared.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
Example 1 to 7: The organic electroluminescent device Produce
An anode was formed of ITO on the substrate on which the reflective layer was formed, and was surface-treated with N 2 plasma or UV-Ozone. HAT-CN was deposited thereon with a hole injection layer (HIL) to a thickness of 100 Å. Subsequently, NPD was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. The electron blocking layer (EBL) was formed to a thickness of 150 Å on the hole transport layer by vacuum evaporation of the compounds of the present invention shown in Table 1 below, and blue EML was formed on the electron blocking layer (EBL) Doped with 2,5-di-, t-butyl-perylene (t-Bu-Perylene) by about 5% with dopant while depositing 9,10-bis (2-naphthyl) anthracene A thick luminescent layer was formed. An electron transport layer (ETL) was deposited to a thickness of 300 Å by mixing an anthracene derivative and LiQ at a weight ratio of 1: 1, and LiQ was deposited thereon as an electron injection layer (EIL) to a thickness of 5 Å. Thereafter, magnesium (Mg) and silver (Ag) were deposited in a thickness of 150 Å at a ratio of 9: 1 to the negative electrode. On the cathode, N4, N4'-Bis [4- [bis (3-methylphenyl) amino] phenyl] -N4, N4'- diphenyl- [1,1'- biphenyl] -4,4'-diamine DNTPD) was deposited to a thickness of 65 nm. A seal cap containing a moisture absorbent with a UV curable adhesive was attached to the capping layer (CPL) to protect the organic electroluminescent device from O 2 or moisture in the air, thereby manufacturing an organic electroluminescent device.
Comparative Example One: The organic electroluminescent device Produce
An organic electroluminescent device was prepared in the same manner as in Example 1, except that TCTA was used instead of the organic compound of the present invention as the electron blocking layer material in Example 1.
Test Example . The organic electroluminescent device Character rating
The characteristics of the organic electroluminescent devices prepared in Examples 1 to 7 and Comparative Example 1 were measured at a current density of 10 mA / cm 2 , and the results are shown in Table 1 below.
(mA / cm 2 )
(V)
(Cd / A)
Claims (9)
[Chemical Formula 1]
In the above formula
R1 is a phenyl group;
R5, R6, R7, R8, and R9 are each a straight chain alkyl group of C1-C4 or a phenyl group, and R2, R3, R4, R5, R6, R7, R8, The rest are all hydrogen.
Wherein the organic compound is any one of the following compounds 1 to 25:
Wherein the organic compound is the following compound 12:
Wherein the organic compound is used as a hole injecting layer material, a hole transporting layer material, an electron blocking layer material, or a light emitting layer material in the material for an organic electroluminescence device.
Wherein at least one of the organic thin film layers contains the organic compound of claim 1 singly or in combination of two or more kinds.
Wherein the organic thin film layer comprises a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer, wherein the organic compound of claim 1 is contained in the hole transporting layer.
Wherein the organic thin film layer includes a hole injecting layer, a hole transporting layer, an electron blocking layer, a light emitting layer, an electron transporting layer, and an electron injecting layer, wherein the organic compound of claim 1 is contained in at least one of the hole transporting layer and the electron blocking layer Wherein the organic electroluminescent device comprises:
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20170056717A (en) | 2015-11-12 | 2017-05-24 | 에스에프씨 주식회사 | organic light-emitting diode with High efficiency |
| CN108603107A (en) * | 2016-02-05 | 2018-09-28 | 默克专利有限公司 | material for electronic device |
| JP2019506368A (en) * | 2015-12-16 | 2019-03-07 | メルク パテント ゲーエムベーハー | Materials for organic electroluminescent devices |
| JP2019506369A (en) * | 2015-12-16 | 2019-03-07 | メルク パテント ゲーエムベーハー | Materials for organic electroluminescent devices |
| WO2019168320A1 (en) * | 2018-02-28 | 2019-09-06 | 주식회사 엘지화학 | Compound and organic light emitting diode comprising same |
| JP2020528445A (en) * | 2017-07-28 | 2020-09-24 | メルク パテント ゲーエムベーハー | Spirobifluorene derivatives for use in electronic devices |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013120577A1 (en) * | 2012-02-14 | 2013-08-22 | Merck Patent Gmbh | Spirobifluorene compounds for organic electroluminescent devices |
-
2014
- 2014-09-30 KR KR1020140131838A patent/KR101555155B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013120577A1 (en) * | 2012-02-14 | 2013-08-22 | Merck Patent Gmbh | Spirobifluorene compounds for organic electroluminescent devices |
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| KR20170056717A (en) | 2015-11-12 | 2017-05-24 | 에스에프씨 주식회사 | organic light-emitting diode with High efficiency |
| US11522136B2 (en) | 2015-11-12 | 2022-12-06 | Sfc Co., Ltd. | Organic light-emitting diode with high efficiency |
| JP7139247B2 (en) | 2015-12-16 | 2022-09-20 | メルク パテント ゲーエムベーハー | Materials for organic electroluminescence devices |
| JP2019506369A (en) * | 2015-12-16 | 2019-03-07 | メルク パテント ゲーエムベーハー | Materials for organic electroluminescent devices |
| JP2019506368A (en) * | 2015-12-16 | 2019-03-07 | メルク パテント ゲーエムベーハー | Materials for organic electroluminescent devices |
| JP2023011548A (en) * | 2015-12-16 | 2023-01-24 | メルク パテント ゲーエムベーハー | Materials for organic electroluminescent devices |
| JP2019507138A (en) * | 2016-02-05 | 2019-03-14 | メルク パテント ゲーエムベーハー | Materials for electronic devices |
| JP7051691B2 (en) | 2016-02-05 | 2022-04-11 | メルク パテント ゲーエムベーハー | Materials for electronic devices |
| CN108603107B (en) * | 2016-02-05 | 2022-08-26 | 默克专利有限公司 | Material for electronic devices |
| CN108603107A (en) * | 2016-02-05 | 2018-09-28 | 默克专利有限公司 | material for electronic device |
| JP2020528445A (en) * | 2017-07-28 | 2020-09-24 | メルク パテント ゲーエムベーハー | Spirobifluorene derivatives for use in electronic devices |
| JP7413252B2 (en) | 2017-07-28 | 2024-01-15 | メルク パテント ゲーエムベーハー | Spirobifluorene derivatives for use in electronic devices |
| WO2019168320A1 (en) * | 2018-02-28 | 2019-09-06 | 주식회사 엘지화학 | Compound and organic light emitting diode comprising same |
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