WO2022090863A1 - 有機化合物、キャリア輸送用材料、ホスト用材料、発光デバイス、発光装置、電子機器および照明装置 - Google Patents
有機化合物、キャリア輸送用材料、ホスト用材料、発光デバイス、発光装置、電子機器および照明装置 Download PDFInfo
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- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- OYQCBJZGELKKPM-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O-2].[Zn+2].[O-2].[In+3] OYQCBJZGELKKPM-UHFFFAOYSA-N 0.000 description 1
- CJGUQZGGEUNPFQ-UHFFFAOYSA-L zinc;2-(1,3-benzothiazol-2-yl)phenolate Chemical compound [Zn+2].[O-]C1=CC=CC=C1C1=NC2=CC=CC=C2S1.[O-]C1=CC=CC=C1C1=NC2=CC=CC=C2S1 CJGUQZGGEUNPFQ-UHFFFAOYSA-L 0.000 description 1
- HTPBWAPZAJWXKY-UHFFFAOYSA-L zinc;quinolin-8-olate Chemical compound [Zn+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 HTPBWAPZAJWXKY-UHFFFAOYSA-L 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
Definitions
- One aspect of the present invention relates to an organic compound, a light emitting element, a light emitting device, a display module, a lighting module, a display device, a light emitting device, an electronic device, and a lighting device. It should be noted that one aspect of the present invention is not limited to the above technical fields.
- the technical field of one aspect of the invention disclosed herein relates to a product, method, or manufacturing method.
- one aspect of the invention relates to a process, machine, manufacture, or composition (composition of matter). Therefore, more specifically, the technical fields of one aspect of the present invention disclosed in the present specification include semiconductor devices, display devices, liquid crystal display devices, light emitting devices, lighting devices, power storage devices, storage devices, image pickup devices, and the like.
- the driving method or the manufacturing method thereof can be given as an example.
- organic EL devices that utilize electroluminescence (EL) using organic compounds
- EL layer organic compound layer
- EL layer organic compound layer
- Such a light emitting device is a self-luminous type, when used as a pixel of a display, it has advantages such as higher visibility than a liquid crystal display and no need for a backlight, and is suitable as an element for a flat panel display. be. Further, it is a great advantage that the display using such a light emitting device can be manufactured thin and lightweight. Another feature is that the response speed is extremely fast.
- these light emitting devices can form the light emitting layer continuously in two dimensions, light emission can be obtained in a planar manner. This is a feature that is difficult to obtain with a point light source represented by an incandescent lamp and an LED, or a line light source represented by a fluorescent lamp, and therefore has high utility value as a surface light source represented by lighting.
- Patent Document 1 discloses a configuration in which an imidazole phenanthridine derivative is used
- Patent Document 2 discloses a configuration in which a triazolophenanthridine derivative is used as a host material for a phosphorescent light emitting device.
- One aspect of the present invention is to provide a novel organic compound.
- another aspect of the invention is to provide a novel host material.
- another aspect of the present invention is to provide a novel organic compound capable of producing a light emitting device having high luminous efficiency.
- another aspect of the present invention is to provide an organic compound capable of providing a light emitting device having a good life.
- another aspect of the present invention is to provide a light emitting device having high luminous efficiency.
- another aspect of the present invention is to provide a light emitting device, a light emitting device, an electronic device, and a display device having low power consumption, respectively.
- another aspect of the present invention is to provide a highly reliable light emitting device, light emitting device, electronic device, and display device, respectively.
- the present invention shall solve any one of the above-mentioned problems.
- an organic substance in which any of a carbazolyl group, a dibenzothiophenyl group, a dibenzofuranyl group and a diarylamino group is bonded to the 3-position of imidazole phenanthridin via an arylene group.
- one aspect of the present invention is an organic compound represented by the following general formula (G1).
- X represents nitrogen or a substituted or unsubstituted carbon
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- R 1 to R 8 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and an substituted or unsubstituted aryl having 6 to 13 carbon atoms. Represents one of the groups.
- A represents a substituted or unsubstituted diarylamino group when X is nitrogen, and when X is carbon, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted carbazolyl group, a substituted or no substituted group.
- another aspect of the present invention is an organic compound in which R1 to R8 are hydrogen in the above configuration.
- one aspect of the present invention is an organic compound represented by the following general formula (G2).
- Z represents oxygen or sulfur
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- R 1 to R 16 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and substituted or unsubstituted alkyl groups having 6 to 13 carbon atoms, respectively. Represents one of the aryl groups.
- another aspect of the present invention is an organic compound in which R 1 to R 16 are hydrogen in the above configuration.
- Another aspect of the present invention is an organic compound represented by the following general formula (G3).
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- R 1 to R 9 and R 20 to R 27 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and a substituted or unsubstituted carbon number. Represents any of 6 to 13 aryl groups.
- another aspect of the present invention is an organic compound in which R 1 to R 9 and R 20 to R 27 are hydrogen in the above configuration.
- another aspect of the present invention is an organic compound in which the Ar is any of the following structural formulas (Ar-1) to (Ar-13) in the above configuration.
- Ar is any of the above structural formulas (Ar-1), (Ar-2), (Ar-7), (Ar-8) and (Ar-10). It is an organic compound which is a group represented by.
- another aspect of the present invention is an organic compound in which Ar is a group represented by the structural formula (Ar-1) in the above configuration.
- another aspect of the present invention is an organic compound represented by the following structural formula (100).
- Another aspect of the present invention is an organic compound represented by the following structural formula (135).
- another aspect of the present invention is a material for a carrier transport layer of a light emitting device containing any of the above organic compounds.
- another aspect of the invention is a host material for a light emitting device comprising any of the above organic compounds.
- another aspect of the present invention comprises an anode, a cathode, and an EL layer located between the anode and the cathode, the EL layer having a light emitting layer, and the light emitting layer.
- a light emitting device having a light emitting material and the above organic compound.
- another aspect of the present invention is an electronic device having the light emitting device and a sensor, an operation button, a speaker, or a microphone.
- another aspect of the present invention is a light emitting device having the above light emitting device, a transistor, or a substrate.
- another aspect of the present invention is a lighting device having the light emitting device and a housing.
- the light emitting device in the present specification includes an image display device using a light emitting device. Further, a module in which a connector, for example, an anisotropic conductive film or TCP (Tape Carrier Package) is attached to the light emitting device, a module in which a printed wiring board is provided at the end of TCP, or a COG (Chip On Glass) method in the light emitting device. A module in which an IC (integrated circuit) is directly mounted may also be included in the light emitting device. In addition, the luminaire may have a light emitting device.
- a connector for example, an anisotropic conductive film or TCP (Tape Carrier Package) is attached to the light emitting device
- a module in which a printed wiring board is provided at the end of TCP or a COG (Chip On Glass) method in the light emitting device.
- COG Chip On Glass
- a module in which an IC (integrated circuit) is directly mounted may also be included in the light emitting device.
- novel organic compounds can be provided.
- a material for a novel carrier transport layer can be provided.
- a novel host material can be provided.
- a host material that can be suitably used for a phosphorescent light emitting device.
- a novel organic compound capable of producing a light emitting device having high luminous efficiency it is possible to provide an organic compound capable of providing a light emitting device having a good life.
- a light emitting device having high luminous efficiency it is possible to provide a light emitting device having high luminous efficiency.
- a light emitting device, a light emitting device, an electronic device, and a display device having low power consumption can be provided.
- a highly reliable light emitting device, light emitting device, electronic device, and display device can be provided.
- FIG. 1A, 1B and 1C are schematic views of the light emitting device.
- 2A and 2B are conceptual diagrams of an active matrix type light emitting device.
- 3A and 3B are conceptual diagrams of an active matrix type light emitting device.
- FIG. 4 is a conceptual diagram of an active matrix type light emitting device.
- 5A and 5B are conceptual diagrams of a passive matrix type light emitting device.
- 6A and 6B are diagrams showing a lighting device.
- 7A, 7B1, 7B2 and 7C are diagrams representing electronic devices.
- 8A, 8B and 8C are diagrams representing electronic devices.
- FIG. 9 is a diagram showing a lighting device.
- FIG. 10 is a diagram showing a lighting device.
- FIG. 11 is a diagram showing an in-vehicle display device and a lighting device.
- FIGS. 12A and 12B are diagrams showing electronic devices.
- 13A, 13B and 13C are diagrams showing electronic devices.
- 14A and 14B are 1 1 1 H NMR charts of DBTPIPt-II.
- FIG. 15 shows an absorption spectrum and an emission spectrum of DBTPIPt-II in a toluene solution.
- FIG. 16 shows an absorption spectrum and an emission spectrum of DBTPIPt-II in a thin film state.
- 17A and 17B are 1 1 H NMR charts of CzPIPt.
- FIG. 18 shows an absorption spectrum and an emission spectrum of CzPIPt in a toluene solution.
- FIG. 19 shows an absorption spectrum and an emission spectrum of CzPIPt in a thin film state.
- FIG. 20A and 20B are 1 H NMR charts of mDPhATPt.
- FIG. 21 shows an absorption spectrum and an emission spectrum of mDPhATPt in a toluene solution.
- FIG. 22 shows an absorption spectrum and an emission spectrum of mDPhATPt in a thin film state.
- FIG. 23 shows the luminance-current density characteristics of the light emitting device 1, the light emitting device 2, the comparative light emitting device 1, and the comparative light emitting device 2.
- FIG. 24 shows the current efficiency-luminance characteristics of the light emitting device 1, the light emitting device 2, the comparative light emitting device 1, and the comparative light emitting device 2.
- FIG. 21 shows an absorption spectrum and an emission spectrum of mDPhATPt in a toluene solution.
- FIG. 22 shows an absorption spectrum and an emission spectrum of mDPhATPt in a thin film state.
- FIG. 23 shows the luminance-current density characteristics of the light emitting device 1, the light emitting device 2, the comparative
- FIG. 25 shows the luminance-voltage characteristics of the light emitting device 1, the light emitting device 2, the comparative light emitting device 1, and the comparative light emitting device 2.
- FIG. 26 shows the current-voltage characteristics of the light emitting device 1, the light emitting device 2, the comparative light emitting device 1, and the comparative light emitting device 2.
- FIG. 27 shows the external quantum efficiency-luminance characteristics of the light emitting device 1, the light emitting device 2, the comparative light emitting device 1, and the comparative light emitting device 2.
- FIG. 28 is an emission spectrum of a light emitting device 1, a light emitting device 2, a comparative light emitting device 1, and a comparative light emitting device 2.
- FIG. 29 shows the normalized luminance-time change characteristics of the light emitting device 1, the light emitting device 2, the comparative light emitting device 1, and the comparative light emitting device 2.
- FIG. 30 shows the luminance-current density characteristics of the light emitting device 3 and the comparative light emitting device 3.
- FIG. 31 shows the current efficiency-luminance characteristics of the light emitting device 3 and the comparative light emitting device 3.
- FIG. 32 shows the luminance-voltage characteristics of the light emitting device 3 and the comparative light emitting device 3.
- FIG. 33 shows the current-voltage characteristics of the light emitting device 3 and the comparative light emitting device 3.
- FIG. 34 shows the external quantum efficiency-luminance characteristics of the light emitting device 3 and the comparative light emitting device 3.
- FIG. 35 shows the brightness-power efficiency characteristics of the light emitting device 3 and the comparative light emitting device 3.
- FIG. 36 is an emission spectrum of the light emitting device 3 and the comparative light emitting device 3.
- FIG. 37 shows the luminance-current density characteristics of the light emitting device 4 and the comparative light emitting device 4.
- FIG. 38 shows the current efficiency-luminance characteristics of the light emitting device 4 and the comparative light emitting device 4.
- FIG. 39 shows the luminance-voltage characteristics of the light emitting device 4 and the comparative light emitting device 4.
- FIG. 40 shows the current-voltage characteristics of the light emitting device 4 and the comparative light emitting device 4.
- FIG. 41 shows the external quantum efficiency-luminance characteristics of the light emitting device 4 and the comparative light emitting device 4.
- FIG. 42 shows the brightness-power efficiency characteristics of the light emitting device 4 and the comparative light emitting device 4.
- FIG. 43 is an emission spectrum of the light emitting device 4 and the comparative light emitting device 4.
- FIG. 44 shows the luminance-current density characteristics of the light emitting device 5 and the comparative light emitting device 5.
- FIG. 45 shows the current efficiency-luminance characteristics of the light emitting device 5 and the comparative light emitting device 5.
- FIG. 46 shows the luminance-voltage characteristics of the light emitting device 5 and the comparative light emitting device 5.
- FIG. 47 shows the current-voltage characteristics of the light emitting device 5 and the comparative light emitting device 5.
- FIG. 48 shows the external quantum efficiency-luminance characteristics of the light emitting device 5 and the comparative light emitting device 5.
- FIG. 49 shows the brightness-power efficiency characteristics of the light emitting device 5 and the comparative light emitting device 5.
- FIG. 50 is an emission spectrum of the light emitting device 5 and the comparative light emitting device 5.
- the organic compound according to one aspect of the present invention is an organic compound represented by the following general formula (G1).
- X represents nitrogen or substituted or unsubstituted carbon.
- the substituents include an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and a substituted or unsubstituted alkyl group having 6 to 6 carbon atoms. It is assumed that any of the 13 aryl groups is substituted.
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- R 1 to R 8 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and an substituted or unsubstituted aryl having 6 to 13 carbon atoms. Represents one of the groups.
- A represents a substituted or unsubstituted diarylamino group when X is nitrogen, and when X is carbon, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted carbazolyl group, a substituted or no substituted group.
- the aryl group of the diarylamino group is a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and specifically, each of them independently contains a phenyl group, a naphthyl group, a biphenyldiyl group, and a fluorenyl group. Can be mentioned.
- the organic compounds represented by the above general formula (G1) are cost-effective because they are easy to synthesize and easy to procure raw materials. ..
- X is carbon and A is a dibenzothiophenyl group or a dibenzofuranyl group.
- A is a dibenzothiophenyl group or a dibenzofuranyl group.
- the dibenzothiophenyl group or the dibenzofuranyl group is bonded to Ar at the 4-position, and the organic compound represented by the following general formula (G2) is preferable.
- Z represents oxygen or sulfur.
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- R 1 to R 16 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and an substituted or unsubstituted aryl group having 6 to 13 carbon atoms. Represents one of.
- the organic compounds represented by the general formula (G2) are cost-effective because they are easy to synthesize and easy to procure raw materials. ..
- the organic compound represented by the general formula (G1) when X is carbon and A is a carbazolyl group, hole transportability is good, which is preferable.
- the carbazolyl group is preferably bonded to the nitrogen Ar at the 9-position, that is, the organic compound represented by the following general formula (G3) is preferable.
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- R 1 to R 9 and R 20 to R 27 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and a substituted or unsubstituted carbon number. Represents any of 6 to 13 aryl groups.
- the organic compounds represented by the general formula (G3) are easy to synthesize and easy to procure raw materials. It is advantageous in terms of cost.
- examples of the arylene group having 6 to 12 carbon atoms represented by Ar include a phenylene group, a naphthylene group, a biphenyldiyl group and the like.
- an organic compound which is any of the groups represented by the following structural formulas (Ar-1) to (Ar-13) is preferable.
- Ar is a group represented by the following structural formulas (Ar-1), (Ar-2), (Ar-7), (Ar-8) and (Ar-10). It is particularly preferable because it is expensive and the raw material is inexpensive, and it is particularly preferable that the group is represented by the following structural formula (Ar-1).
- the substituent that the group and the skeleton can have includes an alkyl group having 1 to 6 carbon atoms and carbon. Examples thereof include a cyclic alkyl group having 3 to 7 carbon atoms and an aryl group having 6 to 13 carbon atoms. As for these substituents, adjacent substituents may form a ring.
- the alkyl group having 1 to 6 carbon atoms is specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, and a hexyl.
- the group can be mentioned.
- Examples of the cyclic alkyl group having 3 to 7 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-methylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
- Examples of the aryl group having 6 to 13 carbon atoms include a phenyl group, a naphthyl group, a biphenyl group, and a fluorenyl group.
- Examples of the alkyl group having 1 to 6 carbon atoms, the cyclic alkyl group having 3 to 7 carbon atoms, and the aryl group having 6 to 13 carbon atoms have the following structural formulas (R-2) to (R-32).
- the group represented by is preferable.
- the organic compound of one aspect of the present invention having the above-mentioned configuration in a light-emitting device, it is possible to provide a light-emitting device having good luminous efficiency. Further, it becomes possible to provide a light emitting device having a good life. Further, the organic compound according to one aspect of the present invention is an organic compound that can be suitably used as a material for a carrier transport layer and a material for a host.
- the organic compound of one aspect of the present invention represented by the above general formula (G1) is a 1,2,4-triazolo [4,3-f] phenanthridin derivative.
- it can be obtained by coupling boronic acid (Compound 2) by the Suzuki-Miyaura reaction.
- X represents nitrogen or carbon.
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- R 1 to R 8 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and an substituted or unsubstituted aryl group having 6 to 13 carbon atoms. Represents one of.
- A represents a substituted or unsubstituted diarylamino group when X is N, a substituted or unsubstituted carbazolyl group when X is carbon, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzo.
- R 50 and R 51 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and R 50 and R 51 are bonded to each other to form a ring. May be.
- X 11 represents a halogen or triflate group.
- the reaction represented by the synthesis scheme (A-1) is carried out by the Suzuki-Miyaura reaction
- the palladium catalyst is palladium (II) acetate or tetrakis (triphenylphosphine) palladium (0).
- the palladium catalyst is palladium (II) acetate or tetrakis (triphenylphosphine) palladium (0).
- bis (triphenylphosphine) palladium (II) dichloride, etc. but other catalysts effective in carrying out this reaction may be used.
- the palladium-catalyzed ligand that can be used in the above synthesis include tri (ortho-tolyl) phosphine, triphenylphosphine, and tricyclohexylphosphine.
- other palladium-catalyzed ligands effective for this reaction may be used.
- the base that can be used in the reaction include an organic base typified by sodium tert-butoxide, potassium carbonate, an inorganic base typified by sodium carbonate, and the like, but other bases can also be used.
- the reaction represented by the synthesis scheme (A-1) is preferably carried out using a solvent.
- the solvent that can be used in the reaction includes a mixed solvent of toluene and water, a mixed solvent of alcohol and water represented by toluene and ethanol, a mixed solvent of xylene and water, and an alcohol and water represented by xylene and ethanol. Examples thereof include a mixed solvent of benzene and water, a mixed solvent of alcohol and water typified by benzene and ethanol, and a mixed solvent of ethers and water typified by ethylene glycol dimethyl ether.
- a mixed solvent of toluene and water, a mixed solvent of toluene and ethanol and water, and a mixed solvent of ethers such as ethylene glycol dimethyl ether and water are more preferable. Further, another solvent effective for this reaction may be used.
- an organoboron compound or boronic acid is used as compound 2 to carry out a cross-coupling reaction.
- the cross-coupling reaction may be carried out using an organic zirconium, an organic zinc, an organic tin compound or the like.
- a halide of the 1,2,4-triazolo [4,3-f] phenanthridine derivative or the imidazo [1,2-f] phenanthridin derivative is used.
- a trifurate substituent (Compound 1) is reacted with an organoboron compound or boronic acid (Compound 2) having an aryl group having a carbazolyl group, a dibenzothiophenyl group, a dibenzofuranyl group or a diarylamino group.
- the organic compound of one aspect of the present invention represented by the following general formula (G2) is a halide or triflate of an imidazo [1,2-f] phenanthridine derivative. It can be obtained by coupling the substituent (Compound 3) with an organic boron compound having a dibenzothiophenyl group or a dibenzofuranyl group, or boronic acid (Compound 4) by the Suzuki-Miyaura reaction.
- Z represents oxygen or sulfur.
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- R 1 to R 9 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and an substituted or unsubstituted aryl group having 6 to 13 carbon atoms.
- R 10 to R 16 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and an substituted or unsubstituted aryl group having 6 to 13 carbon atoms. Represents one of.
- R 52 and R 53 each independently represent hydrogen, one of the alkyl groups having 1 to 6 carbon atoms, and R 52 and R 53 are bonded to each other to form a ring. You may be doing it. Further, X 12 represents a halogen or a triflate group.
- the palladium catalyst is palladium (II) acetate, tetrakis (triphenylphosphine) palladium (0), and bis.
- (Triphenylphosphine) Palladium (II) dichloride and the like can be mentioned, but other catalysts effective in carrying out this reaction may be used.
- the palladium-catalyzed ligand that can be used in the above synthesis include tri (ortho-tolyl) phosphine, triphenylphosphine, and tricyclohexylphosphine.
- a ligand of another palladium catalyst effective in carrying out this reaction may be used.
- the base that can be used in the reaction include an organic base typified by sodium tert-butoxide, potassium carbonate, an inorganic base typified by sodium carbonate, and the like, but other bases may be used.
- the reaction represented by the synthesis scheme (A-2) is preferably carried out using a solvent.
- the solvent that can be used in the reaction includes a mixed solvent of toluene and water, a mixed solvent of alcohol and water represented by toluene and ethanol, a mixed solvent of xylene and water, and an alcohol and water represented by xylene and ethanol. Examples thereof include a mixed solvent of benzene and water, a mixed solvent of alcohol and water typified by benzene and ethanol, and a mixed solvent of ethers and water typified by ethylene glycol dimethyl ether.
- a mixed solvent of toluene and water, a mixed solvent of toluene and ethanol and water, and a mixed solvent of ethers and water typified by ethylene glycol dimethyl ether are more preferable. Further, another solvent effective for this reaction may be used.
- an organoboron compound or boronic acid is used as the compound 4 to carry out a cross-coupling reaction.
- the cross-coupling reaction may be carried out using an organic zirconium, an organic zinc, an organic tin compound or the like.
- a halide or a triflate substituent (Compound 3) of an imidazo [1,2-f] phenanthridin derivative and a dibenzothiophenyl group or dibenzofuranyl are used.
- the organic boron compound or boronic acid (Compound 4) of the group is reacted, but the organic boron compound or boronic acid of the imidazo [1,2-f] phenanthridin derivative is reacted with the dibenzothiophenyl group or the dibenzofuranyl group.
- a halide or a trifurate substituent may be reacted.
- the organic compound of one aspect of the present invention represented by the following general formula (G3) is a halide or triflate of an imidazo [1,2-f] phenanthridine derivative, as shown in the synthesis scheme (A-3). It can be obtained by coupling the substituent (Compound 5) and the carbazole derivative (Compound 6) by the Hartwick-Buchwald reaction.
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- R 1 to R 9 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and an substituted or unsubstituted aryl group having 6 to 13 carbon atoms.
- R 20 to R 27 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and an substituted or unsubstituted aryl group having 6 to 13 carbon atoms.
- X 13 represents a halogen or a triflate group.
- the reaction represented by the synthesis scheme (A-3) is carried out by the Hartwick-Buchwald reaction, it is preferable to use a palladium catalyst, and the palladium catalyst is bis (dibenzylideneacetone) palladium (0) and palladium acetate. (II) and the like can be mentioned.
- the palladium catalyst ligand that can be used in the above synthesis include tri (tert-butyl) phosphine, tri (n-hexyl) phosphine, and tricyclohexylphosphine.
- the base that can be used in the reaction include an organic base typified by sodium tert-butoxide, an inorganic base typified by potassium carbonate, and the like.
- reaction represented by the synthesis scheme (A-3) is preferably carried out using a solvent.
- solvent examples include toluene, xylene, benzene, tetrahydrofuran and the like.
- the organic compound of one aspect of the present invention represented by the following general formula (G4) is a 1,2,4-triazolo [4,3-f] phenanthridin derivative as shown in the synthesis scheme (A-4).
- it can be obtained by coupling a halide of an imidazo [1,2-f] phenanthridine derivative or a triflate substituent (compound 7) with a diarylamine derivative (compound 8) by a Hartwick-Buchwald reaction. can.
- X represents either nitrogen or carbon. When X is carbon, X may have a substituent.
- Ar represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.
- Ar 1 and Ar 2 each independently represent either a substituted or unsubstituted aryl group having 6 to 13 carbon atoms.
- R 1 to R 8 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, and an substituted or unsubstituted aryl group having 6 to 13 carbon atoms. Represents one of.
- X 14 represents a halogen or a triflate group.
- the reaction represented by the synthesis scheme (A-4) is carried out by the Hartwick-Buchwald reaction, it is preferable to use a palladium catalyst, and the palladium catalyst is bis (dibenzylideneacetone) palladium (0) or palladium acetate. (II) and the like can be mentioned.
- the palladium catalyst ligand that can be used in the above synthesis include tri (tert-butyl) phosphine, tri (n-hexyl) phosphine, and tricyclohexylphosphine.
- the base that can be used in the reaction include an organic base typified by sodium tert-butoxide, an inorganic base typified by potassium carbonate, and the like.
- reaction represented by the synthesis scheme (A-4) is preferably carried out using a solvent.
- solvent examples include toluene, xylene, benzene, tetrahydrofuran and the like.
- FIG. 1A shows a diagram showing a light emitting device according to an aspect of the present invention.
- the light emitting device of one aspect of the present invention has a first electrode 101, a second electrode 102, and an EL layer 103. Further, the EL layer 103 has the organic compound shown in the first embodiment.
- the EL layer 103 has a light emitting layer 113, and the light emitting layer 113 contains a light emitting material.
- the organic compound according to the first embodiment is preferably used as a material for dispersing the light emitting material in the light emitting layer 113.
- the light emitting layer 113 may contain other materials.
- the light emitting layer 113 may be configured to co-deposit the organic compound according to the first embodiment and the hole transport material. Further, at this time, the organic compound according to the first embodiment and the hole transporting material may be configured to form an excited complex. By forming an excitation complex having an appropriate emission wavelength, it is possible to realize effective energy transfer to a light emitting material and provide a light emitting device having high efficiency and good lifetime.
- the hole injection layer 111, the hole transport layer 112, the electron transport layer 114, and the electron injection layer 115 are shown in the EL layer 103, but the configuration of the light emitting device is shown. Is not limited to these. It is not necessary to form any of these layers, or it may have a layer having another function.
- the organic compound according to the first embodiment has good electron transport properties, it is also effective to use it for the electron transport layer 114.
- the light emitting device of one aspect of the present invention has an EL layer 103 composed of a plurality of layers between the pair of electrodes of the first electrode 101 and the second electrode 102, and the EL layer 103. Any portion contains the organic compound disclosed in Embodiment 1.
- the first electrode 101 is preferably formed by using a metal having a large work function (specifically, 4.0 eV or more), an alloy, a conductive compound, a mixture thereof, or the like.
- a metal having a large work function specifically, 4.0 eV or more
- an alloy e.g., aluminum, copper, magnesium, magnesium, magnesium, or the like.
- ITO Indium Tin Oxide
- indium-tin oxide containing silicon or silicon oxide indium-zinc oxide-zinc oxide
- tungsten oxide and indium oxide containing zinc oxide specifically, for example. IWZO
- These conductive metal oxide films are usually formed by a sputtering method, but may be produced by applying a sol-gel method or the like.
- indium oxide-zinc oxide may be formed by a sputtering method using a target in which 1 to 20 wt% zinc oxide is added to indium oxide.
- Indium oxide (IWZO) containing tungsten oxide and zinc oxide is formed by a sputtering method using a target containing 0.5 to 5 wt% of tungsten oxide and 0.1 to 1 wt% of zinc oxide with respect to indium oxide. You can also do it.
- nitride of a metallic material for example, titanium nitride
- the electrode material can be selected regardless of the work function.
- the EL layer 103 preferably has a laminated structure.
- the laminated structure is not particularly limited, and various layer structures such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a carrier block layer, an exciton block layer, and a charge generation layer are used. Can be applied.
- FIG. 1A a configuration having an electron transport layer 114 and an electron injection layer 115 in addition to the hole injection layer 111, the hole transport layer 112, and the light emitting layer 113, and FIG. 1B are shown.
- two types of configurations including the electron transport layer 114 and the charge generation layer 116 in addition to the hole injection layer 111, the hole transport layer 112, and the light emitting layer 113 will be described.
- the materials constituting each layer are specifically shown below.
- the hole injection layer 111 is a layer containing a substance having acceptability.
- a substance having acceptability both an organic compound and an inorganic compound can be used.
- a compound having an electron-withdrawing group (halogen group, cyano group, etc.) can be used, and 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquino can be used.
- Dimethane (abbreviation: F4-TCNQ), chloranyl, 2,3,6,7,10,11 - hexaciano-1,4,5,8,9,12-hexazatriphenylene (abbreviation: HAT-CN), 1,3,4,5,7,8-Hexafluorotetracyano-naphthoquinodimethane (abbreviation: F6-TCNNQ), 2- (7-dicyanomethylene-1,3,4,5,6,8,9 , 10-Octafluoro-7H-pyrene-2-iriden) Malononitrile and the like can be mentioned.
- HAT-CN 1,3,4,5,7,8-Hexafluorotetracyano-naphthoquinodimethane
- F6-TCNNQ 2- (7-dicyanomethylene-1,3,4,5,6,8,9 , 10-Octafluoro-7H-pyrene-2-iriden
- a compound such as HAT-CN in which an electron-withdrawing group is bonded to a condensed aromatic ring having a plurality of complex atoms is thermally stable and preferable.
- the [3] radialene derivative having an electron-withdrawing group is preferable because it has very high electron acceptability, and specifically, ⁇ , ⁇ ', ⁇ '.
- transition metal oxides typified by molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, and manganese oxide can be used as the substance having acceptability. ..
- phthalocyanine-based complex compounds typified by phthalocyanine (abbreviation: H 2 Pc) and copper phthalocyanine (CuPc), 4,4'-bis [N- (4-diphenylaminophenyl) -N-phenylamino] biphenyl.
- DPAB N, N'-bis ⁇ 4- [bis (3-methylphenyl) amino] phenyl ⁇ -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine
- DNTPD aromatic amine compound
- PEDOT poly(styrene sulfonic acid)
- Layer 111 can be formed.
- the acceptable substance can extract electrons from the adjacent hole transport layer (or hole transport material) by applying an electric field.
- a composite material in which the acceptable substance is contained in a material having a hole transport property can also be used.
- a composite material containing an acceptor-like substance in a material having a hole-transporting property it is possible to select a material for forming an electrode regardless of a work function. That is, not only a material having a large work function but also a material having a small work function can be used as the first electrode 101.
- the material having a hole transport property used for the composite material various organic compounds such as an aromatic amine compound, a carbazole derivative, an aromatic hydrocarbon, and a polymer compound (oligomer, dendrimer, polymer) can be used.
- the hole-transporting material used for the composite material is preferably a substance having a hole mobility of 1 ⁇ 10 -6 cm 2 / Vs or more. In the following, organic compounds that can be used as materials having hole transport properties in composite materials are specifically listed.
- DTDPPA N'-di (p-tolyl) -N, N'-diphenyl-
- carbazole derivative examples include 3- [N- (9-phenylcarbazole-3-yl) -N-phenylamino] -9-phenylcarbazole (abbreviation: PCzPCA1) and 3,6-bis [N-.
- PCzPCA2 (9-phenylcarbazole-3-yl) -9-phenylamino] -9-phenylcarbazole
- PCzPCN1 4,4'-di (N-carbazolyl) biphenyl
- CBP 4,4'-di (N-carbazolyl) biphenyl
- TCPB 4,4'-di (N-carbazolyl) biphenyl
- TCPB 1,3,5-tris [4- (N-carbazolyl) phenyl] benzene
- TCPB 9- [4- (10-phenyl-9-anthrasenyl) phenyl] -9H-carbazole
- CzPA 1,4-bis [4- (N-carbazolyl) phenyl] -2,3 , 5,6-tetraphenylbenzene and the like
- aromatic hydrocarbon examples include 2-tert-butyl-9,10-di (2-naphthyl) anthracene (abbreviation: t-BuDNA) and 2-tert-butyl-9,10-di (1-naphthyl).
- pentacene, coronene and the like can also be used. It may have a vinyl skeleton.
- aromatic hydrocarbons having a vinyl group include 4,4'-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi) and 9,10-bis [4- (2,2-).
- poly (N-vinylcarbazole) (abbreviation: PVK), poly (4-vinyltriphenylamine) (abbreviation: PVTPA), poly [N- (4- ⁇ N'-[4- (4-diphenylamino)) Phenyl] phenyl-N'-phenylamino ⁇ phenyl) methacrylicamide] (abbreviation: PTPDMA), poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) benzidine] (abbreviation: A polymer compound typified by Poly-TPD) can also be used.
- the hole-transporting material used for the composite material it is more preferable to have any one of a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton and an anthracene skeleton.
- a carbazole skeleton a dibenzofuran skeleton, a dibenzothiophene skeleton and an anthracene skeleton.
- an aromatic amine having a substituent containing a dibenzofuran ring or a dibenzothiophene ring an aromatic monoamine having a naphthalene ring, or an aromatic monoamine in which a 9-fluorenyl group is bonded to the nitrogen of the amine via an arylene group.
- these second organic compounds are substances having an N, N-bis (4-biphenyl) amino group because a light emitting device having a good life can be produced.
- Specific examples of the second organic compound as described above include N- (4-biphenyl) -6, N-diphenylbenzo [b] naphtho [1,2-d] furan-8-amine (abbreviation: abbreviation:).
- BnfABP N, N-bis (4-biphenyl) -6-phenylbenzo [b] naphtho [1,2-d] furan-8-amine
- BBABnf 4,4'-bis (6-phenyl) Benzo [b] naphtho [1,2-d] furan-8-yl) -4''-phenyltriphenylamine
- BnfBB1BP 4,4'-bis (6-phenyl) Benzo [b] naphtho [1,2-d] furan-8-yl) -4''-phenyltriphenylamine
- BnfBB1BP N, N-bis (4-biphenyl) benzo [b] naphtho [1] , 2-d] furan-6-amine
- BBABnf N, N-bis (4-biphenyl) benzo [b] naphtho [1,2-d] furan-8-amine
- BBABnf (8)
- the hole-transporting material used for the composite material is more preferably a substance having a relatively deep HOMO level of ⁇ 5.7 eV or more and ⁇ 5.4 eV or less. Since the hole-transporting material used for the composite material has a relatively deep HOMO level, it is easy to inject holes into the hole-transporting layer 112, and a light-emitting device having a good life can be obtained. Becomes easier.
- the refractive index of the layer can be lowered by further mixing the composite material with a fluoride of an alkali metal or an alkaline earth metal (preferably, the atomic ratio of fluorine atoms in the layer is 20% or more). can. Also by this, a layer having a low refractive index can be formed inside the EL layer 103, and the external quantum efficiency of the light emitting device can be improved.
- the hole injection layer 111 By forming the hole injection layer 111, the hole injection property is improved, and a light emitting device having a small drive voltage can be obtained. Further, the organic compound having acceptability is an easy-to-use material because it is easy to deposit and form a film.
- the hole transport layer 112 is formed containing a material having a hole transport property.
- a material having a hole transport property it is preferable to have a hole mobility of 1 ⁇ 10 -6 cm 2 / Vs or more.
- the material having a hole transport property include 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPB) and N, N'-bis (3-methylphenyl).
- mmDBFFLBi-II compounds having a furan skeleton such as 4- ⁇ 3- [3- (9-phenyl-9H-fluorene-9-yl) phenyl] phenyl ⁇ dibenzofuran
- the compound having an aromatic amine skeleton and the compound having a carbazole skeleton are preferable because they have good reliability, high hole transportability, and contribute to reduction of driving voltage.
- the substance mentioned as the material having hole transportability used for the composite material of the hole injection layer 111 can also be suitably used as the material constituting the hole transport layer 112.
- the light emitting layer 113 has a light emitting substance and a host material.
- the light emitting layer 113 may contain other materials at the same time. Further, two layers having different compositions may be laminated.
- the luminescent substance may be a fluorescent luminescent substance, a phosphorescent luminescent substance, a substance exhibiting thermal activated delayed fluorescence (TADF), or another luminescent substance.
- TADF thermal activated delayed fluorescence
- Examples of the material that can be used as the fluorescent light emitting substance in the light emitting layer 113 include 5,6-bis [4- (10-phenyl-9-anthryl) phenyl] -2,2'-bipyridine (abbreviation: PAP2BPy).
- condensed aromatic diamine compounds typified by pyrenediamine compounds such as 1,6FLPAPrn, 1,6 mMlemFLPARn, and 1,6BnfAPrn-03 are preferable because they have high hole trapping properties and excellent luminous efficiency and reliability. Further, other fluorescent light emitting substances can also be used.
- a phosphorescent light emitting substance is used as the light emitting substance in the light emitting layer 113, as a material that can be used, for example, Tris ⁇ 2- [5- (2-methylphenyl) -4- (2,6-dimethylphenyl) -4- (2,6-dimethylphenyl) ) -4H-1,2,4-triazole-3-yl- ⁇ N2] phenyl- ⁇ C ⁇ iridium (III) (abbreviation: [Ir (mpptz-dmp) 3 ]), Tris (5-methyl-3,4- Diphenyl-4H-1,2,4-triazolat) Iridium (III) (abbreviation: [Ir (Mptz) 3 ]), Tris [4- (3-biphenyl) -5-isopropyl-3-phenyl-4H-1, An organic metal iridium complex having a 4H-triazole skeleton, such as 2,4-triazolate] irid
- Tris (4-methyl-6-phenylpyrimidinat) iridium (III) (abbreviation: [Ir (mppm) 3 ]), Tris (4-t-butyl-6-phenylpyrimidinat) iridium (III).
- organometallic iridium complex having a pyrimidine skeleton is particularly preferable because it is remarkably excellent in reliability and luminous efficiency.
- Iridium (III) (abbreviation: [Ir (tppr) 2 (acac)]), Bis (2,3,5-triphenylpyrazinato) (Dipivaloylmethanato) Iridium (III) ( Abbreviation: [Ir (tppr) 2 (dpm)]), (Acetylacetonato) bis [2,3-bis (4-fluorophenyl) quinoxalinato] Iridium (III) (abbreviation: [Ir (Fdpq) 2 (acac)) ])
- organic metal iridium complexes with a pyridine skeleton such as isoquinolinato-N, C 2' ) i
- organometallic iridium complex having a pyrazine skeleton can obtain red light emission with good chromaticity.
- known phosphorescent luminescent substances may be selected and used.
- TADF material fullerene and its derivatives, acridine and its derivatives, eosin derivatives and the like can be used.
- metal-containing porphyrin include a protoporphyrin-tin fluoride complex (SnF 2 (Proto IX)), a mesoporphyrin-tin fluoride complex (SnF 2 (Meso IX)) and hematoporphyrin represented by the following structural formulas.
- Heterocyclic compounds having one or both aromatic rings can also be used. Since the heterocyclic compound has a ⁇ -electron excess type heteroaromatic ring and a ⁇ -electron deficiency type heteroaromatic ring, both electron transportability and hole transportability are high, which is preferable.
- the skeletons having a ⁇ -electron deficient heteroaromatic ring the pyridine skeleton, the diazine skeleton (pyrimidine skeleton, pyrazine skeleton, pyridazine skeleton), and triazine skeleton are preferable because they are stable and have good reliability.
- the benzoflopyrimidine skeleton, the benzothienopyrimidine skeleton, the benzoflopyrazine skeleton, and the benzothienopyrazine skeleton are preferable because they have high acceptability and good reliability.
- the skeletons having a ⁇ -electron-rich complex aromatic ring the acridine skeleton, the phenoxazine skeleton, the phenothiazine skeleton, the furan skeleton, the thiophene skeleton, and the pyrrole skeleton are stable and have good reliability, and therefore at least one of the skeletons. It is preferable to have.
- the furan skeleton is preferably a dibenzofuran skeleton
- the thiophene skeleton is preferably a dibenzothiophene skeleton.
- the pyrrole skeleton an indole skeleton, a carbazole skeleton, an indolecarbazole skeleton, a bicarbazole skeleton, and a 3- (9-phenyl-9H-carbazole-3-yl) -9H-carbazole skeleton are particularly preferable.
- the substance in which the ⁇ -electron-rich heteroaromatic ring and the ⁇ -electron-deficient heteroaromatic ring are directly bonded has both the electron donating property of the ⁇ -electron-rich heteroaromatic ring and the electron acceptability of the ⁇ -electron-deficient heteroaromatic ring. It becomes stronger and the energy difference between the S1 level and the T1 level becomes smaller, which is particularly preferable because the heat-activated delayed fluorescence can be efficiently obtained.
- an aromatic ring to which an electron-withdrawing group such as a cyano group is bonded may be used.
- ⁇ -electron excess type skeleton an aromatic amine skeleton, a phenazine skeleton, or the like can be used.
- ⁇ -electron-deficient skeletons xanthene skeletons, thioxanthene dioxide skeletons, oxadiazole skeletons, triazole skeletons, imidazole skeletons, anthraquinone skeletons, phenylborane, boron-containing skeletons typified by borantrene, benzonitrile or cyanobenzene can be used.
- An aromatic ring having a nitrile group or a cyano group, a heteroaromatic ring, a carbonyl skeleton typified by benzophenone, a phosphin oxide skeleton, a sulfone skeleton and the like can be used.
- a ⁇ -electron-deficient skeleton and a ⁇ -electron-rich skeleton can be used in place of at least one of the ⁇ -electron-deficient heteroaromatic ring and the ⁇ -electron-rich heteroaromatic ring.
- the TADF material is a material having a small difference between the S1 level and the T1 level and having a function of converting energy from triplet excitation energy to singlet excitation energy by crossing between inverse terms. Therefore, the triplet excited energy can be up-converted to the singlet excited energy (intersystem crossing) with a small amount of thermal energy, and the singlet excited state can be efficiently generated. In addition, triplet excitation energy can be converted into light emission.
- an excited complex also referred to as an exciplex, an exciplex or an Exciplex
- the difference between the S1 level and the T1 level is extremely small, and the triplet excitation energy is the singlet excitation energy. It has a function as a TADF material that can be converted into.
- a phosphorescence spectrum observed at a low temperature may be used.
- a tangent line is drawn at the hem on the short wavelength side of the fluorescence spectrum
- the energy of the wavelength of the extrawire is set to the S1 level
- a tangent line is drawn at the hem on the short wavelength side of the phosphorescent spectrum, and the extrapolation thereof is performed.
- the difference between S1 and T1 is preferably 0.3 eV or less, and more preferably 0.2 eV or less.
- the S1 level of the host material is higher than the S1 level of the TADF material. Further, it is preferable that the T1 level of the host material is higher than the T1 level of the TADF material.
- various carrier transport materials such as a material having an electron transport property, a material having a hole transport property, and the TADF material can be used.
- an organic compound having an amine skeleton or a ⁇ -electron excess type heteroaromatic ring skeleton is preferable.
- NPB 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
- TPD N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [ 1,1'-biphenyl] -4,4'-diamine
- TPD 1,1'-biphenyl] -4,4'-diamine
- BSPB 4,4'-bis [N- (spiro-9,9'-bifluoren-2-yl) -N-phenylamino] biphenyl
- BPAFLP 4-phenyl-4'-(9-phenylfluoren-9-yl) triphenylamine
- BPAFLP 4-phenyl-3'-(9-phenylfluoren-9-yl) tri Pheny
- Examples of the material having electron transportability include bis (10-hydroxybenzo [h] quinolinato) berylium (II) (abbreviation: BeBq 2 ) and bis (2-methyl-8-quinolinolato) (4-phenylphenolato).
- Examples of the organic compound having a ⁇ -electron-deficient heterocyclic ring skeleton include 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD).
- Heterocyclic compound having a diazine skeleton such as [3- (dibenzothiophen-4-yl) phenyl] -benzo [h] quinazoline (abbreviation: 4.8 mDBtP2Bqn), 3,5-bis [3- (9H-carbazole-9) -Il) phenyl] pyridine (abbreviation: 35DCzPPy), and heterocyclic compounds having a pyridine skeleton such as 1,3,5-tri [3- (3-pyridyl) phenyl] benzene (abbreviation: TmPyPB) can be mentioned.
- diazine skeleton such as [3- (dibenzothiophen-4-yl) phenyl] -benzo [h] quinazoline (abbreviation: 4.8 mDBtP2Bqn), 3,5-bis [3- (9H-carbazole-9) -Il) phenyl] pyridine
- the heterocyclic compound having a diazine skeleton or the heterocyclic compound having a pyridine skeleton has good reliability and is preferable.
- a heterocyclic compound having a diazine (pyrimidine, pyrazine, etc.) skeleton has high electron transport property and contributes to reduction of driving voltage.
- the organic compound according to the first embodiment is an organic compound having an electron transport property, and can be suitably used as a host material in a light emitting layer.
- the TADF material that can be used as the host material
- those listed above as the TADF material can also be used in the same manner.
- the triplet excitation energy generated by the TADF material is converted to singlet excitation energy by crossing between inverse terms, and further energy is transferred to the light emitting material, thereby increasing the light emission efficiency of the light emitting device. be able to.
- the TADF material functions as an energy donor and the luminescent material functions as an energy acceptor.
- the S1 level of the TADF material is higher than the S1 level of the fluorescent light emitting substance.
- the T1 level of the TADF material is preferably higher than the S1 level of the fluorescent light emitting substance. Therefore, the T1 level of the TADF material is preferably higher than the T1 level of the fluorescent light emitting substance.
- a TADF material that emits light so as to overlap the wavelength of the absorption band on the lowest energy side of the fluorescent light emitting substance.
- the fluorescent light-emitting substance has a protecting group around the light-emitting group (skeleton that causes light emission) of the fluorescent light-emitting substance.
- a substituent having no ⁇ bond is preferable, a saturated hydrocarbon is preferable, specifically, an alkyl group having 3 or more and 10 or less carbon atoms, and a substituted or unsubstituted cyclo having 3 or more and 10 or less carbon atoms. Examples thereof include an alkyl group and a trialkylsilyl group having 3 or more and 10 or less carbon atoms, and it is more preferable that there are a plurality of protective groups. Since the substituent having no ⁇ bond has a poor function of transporting carriers, the distance between the TADF material and the chromophore of the fluorescent luminescent material can be increased with almost no effect on carrier transport and carrier recombination. ..
- the chromophore refers to an atomic group (skeleton) that causes light emission in a fluorescent luminescent substance.
- the chromophore preferably has a skeleton having a ⁇ bond, preferably contains an aromatic ring, and preferably has a condensed aromatic ring or a condensed complex aromatic ring.
- Examples of the fused aromatic ring or the condensed heteroaromatic ring include a phenanthrene skeleton, a stilbene skeleton, an acridone skeleton, a phenoxazine skeleton, and a phenothiazine skeleton.
- a fluorescent substance having a naphthalene skeleton, anthracene skeleton, fluorene skeleton, chrysene skeleton, triphenylene skeleton, tetracene skeleton, pyrene skeleton, perylene skeleton, coumarin skeleton, quinacridone skeleton, and naphthobisbenzofuran skeleton is preferable because of its high fluorescence quantum yield.
- a material having an anthracene skeleton is suitable as the host material.
- a substance having an anthracene skeleton is used as a host material for a fluorescent light emitting substance, it is possible to realize a light emitting layer having good luminous efficiency and durability.
- a diphenylanthracene skeleton, particularly a substance having a 9,10-diphenylanthracene skeleton is preferable because it is chemically stable.
- the host material has a carbazole skeleton
- HOMO is about 0.1 eV shallower than that of carbazole, holes are easily entered, holes are easily transported, and heat resistance is high, which is suitable. ..
- a substance having a 9,10-diphenylanthracene skeleton and a carbazole skeleton (or a benzocarbazole skeleton or a dibenzocarbazole skeleton) at the same time is further preferable as a host material.
- a benzofluorene skeleton or a dibenzofluorene skeleton may be used instead of the carbazole skeleton.
- examples of such substances are 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole (abbreviation: PCzPA), 3- [4- (1-naphthyl)-.
- Phenyl] -9-Phenyl-9H-carbazole (abbreviation: PCPN), 9- [4- (10-phenyl-9-anthrasenyl) phenyl] -9H-carbazole (abbreviation: CzPA), 7- [4- (10-) Phenyl-9-anthryl) phenyl] -7H-dibenzo [c, g] carbazole (abbreviation: cgDBCzPA), 6- [3- (9,10-diphenyl-2-anthryl) phenyl] -benzo [b] naphtho [1 , 2-d] Fran (abbreviation: 2mBnfPPA), 9-Phenyl-10- ⁇ 4- (9-phenyl-9H-fluoren-9-yl) biphenyl-4'-yl ⁇ anthracene (abbreviation: FLPPA), 9- (1-naphthyl) -10- [4- (2-n
- the host material may be a material obtained by mixing a plurality of kinds of substances, and when a mixed host material is used, it is preferable to mix a material having an electron transport property and a material having a hole transport property. ..
- a material having an electron transport property and a material having a hole transport property By mixing the material having electron transporting property and the material having hole transporting property, the transportability of the light emitting layer 113 can be easily adjusted, and the recombination region can be easily controlled.
- the organic compound according to the first embodiment can be preferably used as the material having electron transportability in the mixed host material.
- the mixing of the material having electron transporting property and the material having hole transporting property may be carried out by co-depositing or by thin-filming a premixed (premixed) sample.
- the organic compound according to the first embodiment is also suitable for mixing in the latter.
- a phosphorescent substance can be used as a part of the mixed material.
- the phosphorescent light-emitting substance can be used as an energy donor that supplies excitation energy to the fluorescent light-emitting substance when the fluorescent light-emitting substance is used as the light-emitting substance.
- an excited complex may be formed between these mixed materials.
- At least one of the materials forming the excitation complex may be a phosphorescent substance.
- the HOMO level of the material having hole transportability is equal to or higher than the HOMO level of the material having electron transportability.
- the LUMO level of the material having hole transportability is equal to or higher than the LUMO level of the material having electron transportability.
- the LUMO level and HOMO level of the material can be derived from the electrochemical properties (reduction potential and oxidation potential) of the material measured by cyclic voltammetry (CV) measurement.
- the emission spectrum of the material having hole transport property, the emission spectrum of the material having electron transport property, and the emission spectrum of the mixed film in which these materials are mixed are compared, and the emission spectrum of the mixed film is compared.
- the transient photoluminescence (PL) of the material having hole transportability, the transient PL of the material having electron transportability, and the transient PL of the mixed membrane in which these materials are mixed are compared, and the transient PL lifetime of the mixed membrane is determined.
- transient PL may be read as transient electroluminescence (EL). That is, the formation of an excited complex can also be formed by comparing the transient EL of the material having hole transportability, the transient EL of the material having electron transportability, and the transient EL of the mixed membrane thereof, and observing the difference in the transient response. You can check.
- EL transient electroluminescence
- the electron transport layer 114 is a layer containing a substance having electron transport properties.
- the substance having electron transporting property the substance listed as the substance having electron transporting property which can be used for the above-mentioned host material can be used.
- the electron transport layer 114 preferably has an electron mobility of 1 ⁇ 10 -7 cm 2 / Vs or more and 5 ⁇ 10 -5 cm 2 / Vs or less when the square root of the electric field strength [V / cm] is 600. By reducing the electron transportability of the electron transport layer 114, the amount of electrons injected into the light emitting layer can be controlled, and the light emitting layer can be prevented from becoming in an electron-rich state. Further, the electron transport layer 114 preferably contains a material having electron transport properties and a simple substance, a compound or a complex of an alkali metal or an alkaline earth metal.
- the hole injection layer is formed as a composite material
- the HOMO level of the material having hole transportability in the composite material is -5.7 eV or more and -5.4 eV or less, which is a relatively deep HOMO level. It is particularly preferable that the substance has a good life. At this time, it is preferable that the HOMO level of the material having electron transportability is ⁇ 6.0 eV or more.
- the material having electron transport property is preferably an organic compound having an anthracene skeleton, and more preferably an organic compound containing both an anthracene skeleton and a heterocyclic skeleton.
- the heterocyclic skeleton is preferably a nitrogen-containing 5-membered ring skeleton or a nitrogen-containing 6-membered ring skeleton, and these heterocyclic skeletons include a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a pyrimidine ring, and a pyridazine. It is particularly preferable to have a nitrogen-containing 5-membered ring skeleton or a nitrogen-containing 6-membered ring skeleton containing two heteroatoms in the ring, such as a ring.
- a simple substance, a compound or a complex of an alkali metal or an alkaline earth metal it is preferable to contain an 8-hydroxyquinolinato structure.
- Specific examples thereof include 8-hydroxyquinolinato-lithium (abbreviation: Liq) and 8-hydroxyquinolinato-sodium (abbreviation: Naq).
- a monovalent metal ion complex, particularly a lithium complex is preferable, and Liq is more preferable.
- a methyl substituted product thereof for example, a 2-methyl substituted product or a 5-methyl substituted product
- a simple substance, a compound or a complex of an alkali metal or an alkaline earth metal has a concentration difference (including the case where it is 0) in the thickness direction thereof.
- lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF 2 ), 8-hydroxyquinolinato-lithium A layer containing an alkali metal or an alkaline earth metal such as typified by (abbreviation: Liq) or a compound thereof may be provided.
- an alkali metal, an alkaline earth metal, or a compound thereof contained in a layer made of a substance having an electron transport property, or an electride may be used. Examples of the electride include a substance in which a high concentration of electrons is added to a mixed oxide of calcium and aluminum.
- the electron-injected layer 115 contains an electron-transporting substance (preferably an organic compound having a bipyridine skeleton) containing fluoride of the alkali metal or alkaline earth metal at a concentration of 50 wt% or more so as to be in a microcrystalline state. It is also possible to use a layer that has been removed. Since the layer has a low refractive index, it is possible to provide a light emitting device having better external quantum efficiency.
- an electron-transporting substance preferably an organic compound having a bipyridine skeleton
- a charge generation layer 116 may be provided instead of the electron injection layer 115 (FIG. 1B).
- the charge generation layer 116 is a layer capable of injecting holes into the layer in contact with the cathode side and electrons into the layer in contact with the anode side by applying an electric potential.
- the charge generation layer 116 includes at least a P-type layer 117.
- the P-type layer 117 is preferably formed by using the composite material mentioned as a material that can form the hole injection layer 111 described above. Further, the P-type layer 117 may be formed by laminating a film containing the above-mentioned acceptor material and a film containing a hole transport material as a material constituting the composite material.
- the organic compound according to one aspect of the present invention is an organic compound having a low refractive index, it is possible to obtain a light emitting device having good external quantum efficiency by using it for the P-type layer 117.
- the charge generation layer 116 is provided with either one or both of the electron relay layer 118 and the electron injection buffer layer 119 in addition to the P-type layer 117.
- the electron relay layer 118 contains at least a substance having electron transportability, and has a function of preventing interaction between the electron injection buffer layer 119 and the P-type layer 117 and smoothly transferring electrons.
- the LUMO level of the electron-transporting substance contained in the electron relay layer 118 is the LUMO level of the accepting substance in the P-type layer 117 and the substance contained in the layer in contact with the charge generating layer 116 in the electron transporting layer 114. It is preferably between the LUMO level.
- the specific energy level of the LUMO level in the electron-transporting substance used for the electron relay layer 118 is preferably ⁇ 5.0 eV or higher, preferably ⁇ 5.0 eV or higher and ⁇ 3.0 eV or lower.
- As the substance having electron transportability used for the electron relay layer 118 it is preferable to use a phthalocyanine-based material or a metal complex having a metal-oxygen bond and an aromatic ligand.
- the electron injection buffer layer 119 includes an alkali metal, an alkaline earth metal, a rare earth metal, and a compound thereof (alkali metal compound (oxide represented by lithium oxide, halide, carbonate represented by lithium carbonate or cesium carbonate).
- alkali metal compound oxide represented by lithium oxide, halide, carbonate represented by lithium carbonate or cesium carbonate.
- the donor substance includes an alkali metal, an alkaline earth metal, a rare earth metal, and a compound thereof (as a donor substance).
- Alkali metal compounds including oxides such as lithium oxide, halides, lithium carbonate, and carbonates such as cesium carbonate
- alkaline earth metal compounds including oxides, halides, and carbonates
- organic compounds typified by tetrathianaphthalene (abbreviation: TTN), nickerosen, and decamethyl nickerosen can also be used.
- TTN tetrathianaphthalene
- nickerosen nickerosen
- decamethyl nickerosen can also be used.
- the substance having electron transportability it can be formed by using the same material as the material constituting the electron transport layer 114 described above.
- a metal having a small work function (specifically, 3.8 eV or less), an alloy, an electrically conductive compound, a mixture thereof, or the like
- a cathode material include an alkali metal typified by lithium (Li) and cesium (Cs), and an elemental periodic table represented by magnesium (Mg), calcium (Ca), and strontium (Sr).
- Mg magnesium
- Ca calcium
- examples thereof include elements belonging to Group 1 or Group 2, rare earth metals typified by alloys containing them (MgAg, AlLi), europium (Eu), ytterbium (Yb), and alloys containing these.
- indium tin oxide containing Al, Ag, ITO, silicon or silicon oxide is provided regardless of the size of the work function.
- Various conductive materials such as, etc. can be used as the second electrode 102. These conductive materials can be formed into a film by using a dry method such as a vacuum vapor deposition method or a sputtering method, an inkjet method, a spin coating method, or the like. Further, it may be formed by a wet method using a sol-gel method, or may be formed by a wet method using a paste of a metal material.
- a method for forming the EL layer 103 various methods can be used regardless of whether it is a dry method or a wet method.
- a vacuum vapor deposition method, a gravure printing method, an offset printing method, a screen printing method, an inkjet method, a spin coating method, or the like may be used.
- each electrode or each layer described above may be formed by using a different film forming method.
- the structure of the layer provided between the first electrode 101 and the second electrode 102 is not limited to the above. However, holes and electrons are located away from the first electrode 101 and the second electrode 102 so that the quenching caused by the proximity of the light emitting region to the metal used for the electrode or carrier injection layer is suppressed. It is preferable to provide a light emitting region in which the electrons are recombined.
- the hole transport layer or the electron transport layer in contact with the light emitting layer 113 suppresses the energy transfer from the excitons generated in the light emitting layer, so that the band gap thereof.
- a light emitting device also referred to as a laminated element or a tandem type element having a configuration in which a plurality of light emitting units are laminated
- This light emitting device is a light emitting device having a plurality of light emitting units between the anode and the cathode.
- One light emitting unit has substantially the same configuration as the EL layer 103 shown in FIG. 1A. That is, it can be said that the light emitting device shown in FIG. 1C is a light emitting device having a plurality of light emitting units, and the light emitting device shown in FIG. 1A or FIG. 1B is a light emitting device having one light emitting unit.
- the organic compound according to the first embodiment may be contained in at least one of a plurality of light emitting units.
- a first light emitting unit 511 and a second light emitting unit 512 are laminated between the anode 501 and the cathode 502, and between the first light emitting unit 511 and the second light emitting unit 512. Is provided with a charge generation layer 513.
- the anode 501 and the cathode 502 correspond to the first electrode 101 and the second electrode 102 in FIG. 1A, respectively, and the same ones described in the description of FIG. 1A can be applied.
- the first light emitting unit 511 and the second light emitting unit 512 may have the same configuration or different configurations.
- the charge generation layer 513 has a function of injecting electrons into one light emitting unit and injecting holes into the other light emitting unit when a voltage is applied to the anode 501 and the cathode 502. That is, in FIG. 1C, when a voltage is applied so that the potential of the anode is higher than the potential of the cathode, the charge generation layer 513 injects electrons into the first light emitting unit 511 and the second light emitting unit. Anything that injects holes into 512 may be used.
- the charge generation layer 513 is preferably formed with the same configuration as the charge generation layer 116 described with reference to FIG. 1B. Since the composite material of the organic compound and the metal oxide is excellent in carrier injection property and carrier transport property, low voltage drive and low current drive can be realized. When the surface of the light emitting unit on the anode side is in contact with the charge generating layer 513, the charge generating layer 513 can also serve as the hole injection layer of the light emitting unit, so that the light emitting unit uses the hole injection layer. It does not have to be provided.
- the electron injection buffer layer 119 plays the role of the electron injection layer in the light emitting unit on the anode side, so that the light emitting unit on the anode side does not necessarily have an electron injection layer. There is no need to form.
- FIG. 1C a light emitting device having two light emitting units has been described, but the same can be applied to a light emitting device in which three or more light emitting units are stacked.
- a light emitting device in which three or more light emitting units are stacked.
- each light emitting unit by making the emission color of each light emitting unit different, it is possible to obtain light emission of a desired color as the entire light emitting device. For example, in a light emitting device having two light emitting units, a light emitting device that emits white light as a whole by obtaining a red and green light emitting color from the first light emitting unit and a blue light emitting color from the second light emitting unit. It is also possible to get it.
- each layer or electrode such as the EL layer 103, the first light emitting unit 511, the second light emitting unit 512 and the charge generation layer may be, for example, a vapor deposition method (including a vacuum vapor deposition method) or a droplet ejection method (inkjet). It can be formed by using a method typified by a method), a coating method, and a gravure printing method. They may also include small molecule materials, medium molecule materials (including oligomers, dendrimers), or polymer materials.
- FIG. 2A is a top view showing a light emitting device
- FIG. 2B is a cross-sectional view of FIG. 2A cut by AB and CD.
- This light emitting device includes a drive circuit unit (source line drive circuit) 601, a pixel unit 602, and a drive circuit unit (gate line drive circuit) 603 shown by dotted lines to control the light emission of the light emitting device.
- 604 is a sealing substrate
- 605 is a sealing material
- the inside surrounded by the sealing material 605 is a space 607.
- the routing wiring 608 is a wiring for transmitting signals input to the source line drive circuit 601 and the gate line drive circuit 603, and is a video signal, a clock signal, and a video signal and a clock signal from the FPC (flexible print circuit) 609 which is an external input terminal. Receives start signal, reset signal, etc. Although only the FPC is shown here, a printed wiring board (PWB) may be attached to the FPC.
- the light emitting device in the present specification includes not only the light emitting device main body but also a state in which an FPC or a PWB is attached to the light emitting device main body.
- a drive circuit unit and a pixel unit are formed on the element substrate 610, and here, a source line drive circuit 601 which is a drive circuit unit and one pixel in the pixel unit 602 are shown.
- the element substrate 610 uses a substrate made of glass, quartz, organic resin, metal, alloy, semiconductor, etc., as well as a plastic substrate made of FRP (Fiber Reinforced Plastics), PVF (polyvinyl flolide), polyester, acrylic resin, etc. It may be produced.
- FRP Fiber Reinforced Plastics
- PVF polyvinyl flolide
- polyester acrylic resin
- the structure of the transistor used in the pixel or the drive circuit is not particularly limited. For example, it may be an inverted stagger type transistor or a stagger type transistor. Further, a top gate type transistor or a bottom gate type transistor may be used.
- the semiconductor material used for the transistor is not particularly limited, and for example, silicon, germanium, silicon carbide, gallium nitride and the like can be used. Alternatively, an oxide semiconductor containing at least one of indium, gallium, and zinc, such as an In-Ga-Zn-based metal oxide, may be used.
- the crystallinity of the semiconductor material used for the transistor is not particularly limited, and either an amorphous semiconductor or a semiconductor having crystallinity (a fine crystal semiconductor, a polycrystalline semiconductor, a single crystal semiconductor, or a semiconductor having a partially crystallized region). May be used. It is preferable to use a semiconductor having crystallinity because deterioration of transistor characteristics can be suppressed.
- an oxide semiconductor in addition to the transistor provided in the pixel or the drive circuit, it is preferable to apply an oxide semiconductor to a semiconductor device typified by a transistor used in a touch sensor or the like described later. In particular, it is preferable to apply an oxide semiconductor having a wider bandgap than silicon. By using an oxide semiconductor having a wider bandgap than silicon, the current in the off state of the transistor can be reduced.
- the oxide semiconductor preferably contains at least indium (In) or zinc (Zn). Further, an oxide semiconductor containing an oxide represented by an In—M—Zn-based oxide (M is a metal typified by Al, Ti, Ga, Ge, Y, Zr, Sn, La, Ce or Hf). It is more preferable to have.
- M is a metal typified by Al, Ti, Ga, Ge, Y, Zr, Sn, La, Ce or Hf. It is more preferable to have.
- the semiconductor layer has a plurality of crystal portions, and the c-axis of the crystal portion is oriented perpendicular to the surface to be formed of the semiconductor layer or the upper surface of the semiconductor layer, and grain boundaries are formed between adjacent crystal portions. It is preferable to use an oxide semiconductor film that does not have.
- the transistor having the above-mentioned semiconductor layer can retain the electric charge accumulated in the capacitance through the transistor for a long period of time due to its low off current.
- the transistor having the above-mentioned semiconductor layer can retain the electric charge accumulated in the capacitance through the transistor for a long period of time due to its low off current.
- a base film in order to stabilize the characteristics of the transistor.
- an inorganic insulating film such as a silicon oxide film, a silicon nitride film, a silicon nitride film, and a silicon nitride film can be used, and can be produced as a single layer or laminated.
- the undercoat uses a sputtering method, a CVD (Chemical Vapor Deposition) method (plasma CVD method, thermal CVD method, MOCVD (Metal Organic CVD) method, etc.), ALD (Atomic Layer Deposition) method, coating method, printing method, etc. Can be formed.
- the undercoat may not be provided if it is not necessary.
- the FET 623 represents one of the transistors formed in the drive circuit unit 601.
- the drive circuit may be formed of various CMOS circuits, epitaxial circuits or MIMO circuits.
- the driver integrated type in which the drive circuit is formed on the substrate is shown, but it is not always necessary, and the drive circuit can be formed on the outside instead of on the substrate.
- the pixel unit 602 is formed by a plurality of pixels including a switching FET 611, a current control FET 612, and a first electrode 613 electrically connected to the drain thereof, but is not limited to 3.
- a pixel unit may be a combination of two or more FETs and a capacitive element.
- An insulator 614 is formed so as to cover the end portion of the first electrode 613.
- it can be formed by using a positive type photosensitive acrylic resin film.
- a curved surface having a curvature is formed at the upper end portion or the lower end portion of the insulating material 614.
- a positive photosensitive acrylic resin is used as the material of the insulating material 614, it is preferable that only the upper end portion of the insulating material 614 has a curved surface having a radius of curvature (0.2 ⁇ m to 3 ⁇ m).
- a negative type photosensitive resin or a positive type photosensitive resin can be used as the insulating material 614.
- An EL layer 616 and a second electrode 617 are formed on the first electrode 613, respectively.
- the material used for the first electrode 613 that functions as an anode it is desirable to use a material having a large work function.
- a laminated structure of a titanium nitride film and a film containing aluminum as a main component, a three-layer structure of a titanium nitride film and a film containing aluminum as a main component, and a titanium nitride film can be used. It should be noted that the laminated structure has low resistance as wiring, good ohmic contact can be obtained, and can further function as an anode.
- the EL layer 616 is formed by various methods typified by a vapor deposition method using a vapor deposition mask, an inkjet method, and a spin coating method.
- the EL layer 616 includes a configuration as described in the second embodiment.
- a low molecular weight compound or a high molecular weight compound may be used as another material constituting the EL layer 616.
- the material used for the second electrode 617 formed on the EL layer 616 and functioning as a cathode a material having a small work function (Al, Mg, Li, Ca, or an alloy or compound thereof (MgAg, MgIn, etc.) It is preferable to use AlLi etc.)).
- the second electrode 617 is a thin metal thin film and a transparent conductive film (ITO, 2 to 20 wt% oxidation). It is preferable to use a laminate with indium oxide containing zinc, indium tin oxide containing silicon, zinc oxide (ZnO), etc.).
- a light emitting device is formed by the first electrode 613, the EL layer 616, and the second electrode 617.
- the light emitting device is the light emitting device according to the second embodiment. Although a plurality of light emitting devices are formed in the pixel portion, in the light emitting device of the present embodiment, both the light emitting device according to the second embodiment and the light emitting device having other configurations are mixed. You may be doing it.
- the sealing substrate 604 by bonding the sealing substrate 604 to the element substrate 610 with the sealing material 605, the light emitting device 618 is provided in the space 607 surrounded by the element substrate 610, the sealing substrate 604, and the sealing material 605.
- the space 607 is filled with a filler, and may be filled with an inert gas (nitrogen, argon, etc.) or a sealing material.
- an epoxy resin or a glass frit for the sealing material 605. Further, it is desirable that these materials are materials that do not allow moisture and oxygen to permeate as much as possible. Further, as a material used for the sealing substrate 604, in addition to a glass substrate and a quartz substrate, a plastic substrate made of FRP (Fiber Reinforced Plastics), PVF (polyvinyl fluoride), polyester, acrylic resin or the like can be used.
- FRP Fiber Reinforced Plastics
- PVF polyvinyl fluoride
- polyester acrylic resin or the like
- a protective film may be provided on the second electrode.
- the protective film may be formed of an organic resin film or an inorganic insulating film. Further, a protective film may be formed so as to cover the exposed portion of the sealing material 605. Further, the protective film can be provided so as to cover the surface and side surfaces of the pair of substrates, the sealing layer, and the exposed side surfaces of the insulating layer.
- the protective film a material typified by water that does not easily permeate impurities can be used. Therefore, it is possible to effectively suppress the diffusion of the above impurities from the outside to the inside.
- oxides, nitrides, fluorides, sulfides, ternary compounds, metals, polymers and the like can be used, and for example, aluminum oxide, hafnium oxide, hafnium silicate, lanthanum oxide and oxidation can be used.
- nitride Materials including hafnium, silicon nitride, tantalum nitride, titanium nitride, niobium nitride, molybdenum nitride, zirconium nitride or gallium nitride, nitrides including titanium and aluminum, oxides containing titanium and aluminum, oxides containing aluminum and zinc , A sulfide containing manganese and zinc, a sulfide containing cerium and strontium, an oxide containing erbium and aluminum, an oxide containing yttrium and zirconium, and the like can be used.
- the protective film is preferably formed by using a film forming method having good step coverage (step coverage).
- a film forming method having good step coverage is the atomic layer deposition (ALD) method.
- ALD atomic layer deposition
- ALD method it is possible to form a protective film having a dense, reduced defects such as cracks or pinholes, or a uniform thickness.
- damage to the processed member when forming the protective film can be reduced.
- the protective film using the ALD method, it is possible to form a uniform protective film with few defects on the front surface having a complicated uneven shape, the upper surface, the side surface and the back surface of the touch panel.
- a light emitting device manufactured by using the light emitting device according to the second embodiment can be obtained.
- the light emitting device in the present embodiment uses the light emitting device according to the second embodiment, it is possible to obtain a light emitting device having good characteristics. Specifically, since the light emitting device according to the second embodiment has good luminous efficiency, it can be a light emitting device having low power consumption.
- FIG. 3 shows an example of a light emitting device in which a light emitting device exhibiting white light emission is formed and a colored layer (color filter) or the like is provided to make it full color.
- FIG. 3A shows a substrate 1001, an underlying insulating film 1002, a gate insulating film 1003, a gate electrode 1006, 1007, 1008, a first interlayer insulating film 1020, a second interlayer insulating film 1021, a peripheral portion 1042, a pixel portion 1040, and a drive.
- the circuit unit 1041, the first electrode of the light emitting device 1024W, 1024R, 1024G, 1024B, the partition wall 1025, the EL layer 1028, the second electrode 1029 of the light emitting device, the sealing substrate 1031, the sealing material 1032, and the like are shown. ..
- the colored layer (red colored layer 1034R, green colored layer 1034G, blue colored layer 1034B) is provided on the transparent base material 1033. Further, a black matrix 1035 may be further provided. The transparent base material 1033 provided with the colored layer and the black matrix is aligned and fixed to the substrate 1001. The colored layer and the black matrix 1035 are covered with the overcoat layer 1036. Further, in FIG. 3A, there is a light emitting layer in which light is emitted to the outside without passing through the colored layer and a light emitting layer in which light is transmitted to the outside through the colored layer of each color. Since the light transmitted through the white and colored layers is red, green, and blue, the image can be expressed by the pixels of four colors.
- FIG. 3B shows an example in which a colored layer (red colored layer 1034R, green colored layer 1034G, blue colored layer 1034B) is formed between the gate insulating film 1003 and the first interlayer insulating film 1020.
- the colored layer may be provided between the substrate 1001 and the sealing substrate 1031.
- the light emitting device has a structure that extracts light to the substrate 1001 side on which the FET is formed (bottom emission type), but has a structure that extracts light to the sealing substrate 1031 side (top emission type). ) May be used as a light emitting device.
- a cross-sectional view of the top emission type light emitting device is shown in FIG.
- the substrate 1001 can be a substrate that does not transmit light.
- the electrode 1022 that connects the FET and the anode of the light emitting device is manufactured, it is formed in the same manner as the bottom emission type light emitting device.
- a third interlayer insulating film 1037 is formed so as to cover the electrode 1022. This insulating film may play a role of flattening.
- the third interlayer insulating film 1037 can be formed by using the same material as the second interlayer insulating film and other known materials.
- the first electrodes 1024W, 1024R, 1024G, and 1024B of the light emitting device are used as an anode here, but may be a cathode. Further, in the case of the top emission type light emitting device as shown in FIG. 4, it is preferable that the first electrode is a reflecting electrode.
- the structure of the EL layer 1028 is the same as that described as the EL layer 103 in the second embodiment, and has an element structure such that white light emission can be obtained.
- the sealing can be performed by the sealing substrate 1031 provided with the colored layer (red colored layer 1034R, green colored layer 1034G, blue colored layer 1034B).
- the sealing substrate 1031 may be provided with a black matrix 1035 so as to be located between the pixels.
- the colored layer (red colored layer 1034R, green colored layer 1034G, blue colored layer 1034B) and the black matrix may be covered with the overcoat layer 1036.
- a substrate having translucency is used as the sealing substrate 1031.
- an example of performing full-color display in four colors of red, green, blue, and white is shown, but the present invention is not particularly limited, and four colors of red, yellow, green, and blue or full-color in three colors of red, green, and blue are shown. It may be displayed.
- the microcavity structure can be preferably applied.
- a light emitting device having a microcavity structure can be obtained by using a first electrode as a reflective electrode and a second electrode as a semi-transmissive / semi-reflective electrode.
- An EL layer is provided between the reflective electrode and the semi-transmissive / semi-reflective electrode, and at least a light emitting layer serving as a light emitting region is provided.
- the reflective electrode is a film having a visible light reflectance of 40% to 100%, preferably 70% to 100%, and a resistivity of 1 ⁇ 10 ⁇ 2 ⁇ cm or less.
- the semi-transmissive / semi-reflective electrode is a film having a visible light reflectance of 20% to 80%, preferably 40% to 70%, and a resistivity of 1 ⁇ 10 ⁇ 2 ⁇ cm or less. ..
- the light emitted from the light emitting layer included in the EL layer is reflected by the reflective electrode and the semi-transmissive / semi-reflective electrode and resonates.
- the light emitting device can change the optical distance between the reflective electrode and the transflective / semi-reflective electrode by changing the thickness of the transparent conductive film, the above-mentioned composite material, the carrier transport material, and the like. As a result, it is possible to intensify the light having a wavelength that resonates between the reflecting electrode and the transflective / semi-reflective electrode, and to attenuate the light having a wavelength that does not resonate.
- the light reflected and returned by the reflecting electrode causes large interference with the light directly incident on the semi-transmissive / semi-reflecting electrode from the light emitting layer (first incident light), and is therefore reflected.
- the EL layer may have a structure having a plurality of light emitting layers or a structure having a single light emitting layer, and may be combined with, for example, the above-mentioned configuration of the tandem type light emitting device.
- a plurality of EL layers may be provided on one light emitting device with a charge generation layer interposed therebetween, and the present invention may be applied to a configuration in which a single or a plurality of light emitting layers are formed in each EL layer.
- the microcavity structure By having the microcavity structure, it is possible to enhance the emission intensity in the front direction of a specific wavelength, so that it is possible to reduce power consumption.
- the microcavity structure that matches the wavelength of each color can be applied to all the sub-pixels in addition to the effect of improving the brightness by yellow light emission. It can be a light emitting device with good characteristics.
- the light emitting device in the present embodiment uses the light emitting device according to the second embodiment, it is possible to obtain a light emitting device having good characteristics. Specifically, since the light emitting device according to the second embodiment has good luminous efficiency, it can be a light emitting device having low power consumption.
- FIG. 5 shows a passive matrix type light emitting device manufactured by applying the present invention.
- 5A is a perspective view showing a light emitting device
- FIG. 5B is a cross-sectional view of FIG. 5A cut by XY.
- an EL layer 955 is provided between the electrode 952 and the electrode 956 on the substrate 951.
- the end of the electrode 952 is covered with an insulating layer 953.
- a partition wall layer 954 is provided on the insulating layer 953.
- the side wall of the partition wall layer 954 has an inclination such that the distance between one side wall and the other side wall becomes narrower as it gets closer to the substrate surface. That is, the cross section in the short side direction of the partition wall layer 954 is trapezoidal, and the bottom side (the side facing the same direction as the surface direction of the insulating layer 953 and in contact with the insulating layer 953) is the upper side (the surface of the insulating layer 953). It faces in the same direction as the direction, and is shorter than the side that does not contact the insulating layer 953).
- the passive matrix type light emitting device also uses the light emitting device according to the second embodiment, and can be a highly reliable light emitting device or a light emitting device having low power consumption.
- the light emitting device described above can control a large number of minute light emitting devices arranged in a matrix, it is a light emitting device that can be suitably used as a display device for expressing an image.
- FIG. 6B is a top view of the lighting device
- FIG. 6A is a sectional view taken along the line ef in FIG. 6B.
- the first electrode 401 is formed on the translucent substrate 400 which is a support.
- the first electrode 401 corresponds to the first electrode 101 in the second embodiment.
- the first electrode 401 is formed of a translucent material.
- a pad 412 for supplying a voltage to the second electrode 404 is formed on the substrate 400.
- the EL layer 403 is formed on the first electrode 401.
- the EL layer 403 corresponds to the configuration of the EL layer 103 in the second embodiment, or the configuration in which the light emitting units 511 and 512 and the charge generation layer 513 are combined. Please refer to the description for these configurations.
- a second electrode 404 is formed by covering the EL layer 403.
- the second electrode 404 corresponds to the second electrode 102 in the second embodiment.
- the second electrode 404 is formed of a material having high reflectance.
- the second electrode 404 is connected to the pad 412 to supply a voltage.
- the lighting device showing the light emitting device having the first electrode 401, the EL layer 403, and the second electrode 404 in the present embodiment has. Since the light emitting device is a light emitting device having high luminous efficiency, the lighting device in the present embodiment can be a lighting device having low power consumption.
- the lighting device is completed by fixing the substrate 400 on which the light emitting device having the above configuration is formed and the sealing substrate 407 using the sealing materials 405 and 406 and sealing them. Either one of the sealing materials 405 and 406 may be used. Further, a desiccant can be mixed with the inner sealing material 406 (not shown in FIG. 6B), whereby moisture can be adsorbed, which leads to improvement in reliability.
- the pad 412 and a part of the first electrode 401 can be used as an external input terminal.
- an IC chip 420 equipped with a converter or the like may be provided on the IC chip 420.
- the lighting device according to the present embodiment uses the light emitting device according to the second embodiment for the EL element, and can be a lighting device having low power consumption.
- the light emitting device according to the second embodiment is a light emitting device having good luminous efficiency and low power consumption.
- the electronic device described in the present embodiment can be an electronic device having a light emitting unit having low power consumption.
- Examples of electronic devices to which the above light emitting device is applied include television devices (also referred to as televisions or television receivers), monitors for computers, digital cameras, digital video cameras, digital photo frames, and mobile phones (mobile phones). , Also referred to as a mobile phone device), a portable game machine, a mobile information terminal, a sound reproduction device, and a large game machine represented by a pachinko machine. Specific examples of these electronic devices are shown below.
- FIG. 7A shows an example of a television device.
- the display unit 7103 is incorporated in the housing 7101. Further, here, a configuration in which the housing 7101 is supported by the stand 7105 is shown. An image can be displayed by the display unit 7103, and the display unit 7103 is configured by arranging the light emitting devices according to the second embodiment in a matrix.
- the operation of the television device can be performed by an operation switch included in the housing 7101 and a separate remote control operation machine 7110.
- the channel and volume can be operated by the operation key 7109 provided in the remote controller 7110, and the image displayed on the display unit 7103 can be operated.
- the remote controller 7110 may be provided with a display unit 7107 for displaying information output from the remote controller 7110.
- the television device is configured to include a receiver, a modem, and the like.
- the receiver can receive general television broadcasts, and by connecting to a wired or wireless communication network via a modem, one-way (sender to receiver) or two-way (sender and receiver). It is also possible to perform information communication between (or between receivers, etc.).
- FIG. 7B1 is a computer, which includes a main body 7201, a housing 7202, a display unit 7203, a keyboard 7204, an external connection port 7205, a pointing device 7206, and the like.
- This computer is manufactured by arranging the light emitting devices according to the second embodiment in a matrix and using them in the display unit 7203.
- the computer of FIG. 7B1 may have the form shown in FIG. 7B2.
- the computer of FIG. 7B2 is provided with a second display unit 7210 instead of the keyboard 7204 and the pointing device 7206.
- the second display unit 7210 is a touch panel type, and input can be performed by operating the input display displayed on the second display unit 7210 with a finger or a dedicated pen.
- the second display unit 7210 can display not only the input display but also other images. Further, the display unit 7203 may also be a touch panel. By connecting the two screens with a hinge, it is possible to prevent troubles such as damage or damage to the screens during storage and transportation.
- FIG. 7C shows an example of a mobile terminal.
- the mobile phone includes an operation button 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like, in addition to the display unit 7402 incorporated in the housing 7401.
- the mobile phone has a display unit 7402 manufactured by arranging the light emitting devices according to the second embodiment in a matrix.
- the mobile terminal shown in FIG. 7C may be configured so that information can be input by touching the display unit 7402 with a finger or a stylus.
- operations such as making a phone call or composing an e-mail can be performed by touching the display unit 7402 with a finger or a stylus.
- the screen of the display unit 7402 mainly has three modes. The first is a display mode mainly for displaying an image, and the second is an input mode mainly for inputting information represented by characters. The third is a display + input mode in which two modes, a display mode and an input mode, are mixed.
- the display unit 7402 may be set to a character input mode mainly for inputting characters, and the characters displayed on the screen may be input. In this case, it is preferable to display the keyboard or the number button on most of the screen of the display unit 7402.
- the orientation (vertical or horizontal) of the mobile terminal can be determined and the screen display of the display unit 7402 can be determined. Can be switched automatically.
- the screen mode can be switched by touching the display unit 7402 or by operating the operation button 7403 of the housing 7401. It is also possible to switch depending on the type of the image displayed on the display unit 7402. For example, if the image signal displayed on the display unit is moving image data, the display mode is switched, and if the image signal is text data, the input mode is switched.
- the input mode the signal detected by the optical sensor of the display unit 7402 is detected, and if there is no input by the touch operation of the display unit 7402 for a certain period of time, the screen mode is switched from the input mode to the display mode. You may control it.
- the display unit 7402 can also function as an image sensor.
- the person can be authenticated by touching the display unit 7402 with a palm or a finger and taking an image of a palm print, a fingerprint, or the like.
- a backlight that emits near-infrared light or a sensing light source that emits near-infrared light is used for the display unit, it is possible to image a finger vein, a palm vein, or the like.
- FIG. 8A is a schematic diagram showing an example of a cleaning robot.
- the cleaning robot 5100 has a display 5101 arranged on the upper surface, a plurality of cameras 5102 arranged on the side surface, a brush 5103, and an operation button 5104. Although not shown, the lower surface of the cleaning robot 5100 is provided with tires, suction ports, and the like.
- the cleaning robot 5100 also includes various sensors such as an infrared sensor, an ultrasonic sensor, an acceleration sensor, a piezo sensor, an optical sensor, or a gyro sensor. Further, the cleaning robot 5100 is provided with a wireless communication means.
- the cleaning robot 5100 is self-propelled, can detect dust 5120, and can suck dust from a suction port provided on the lower surface.
- the cleaning robot 5100 can analyze the image taken by the camera 5102 and determine the presence or absence of an obstacle such as a wall, furniture, or a step. Further, when an object that is likely to be entangled with the brush 5103 such as wiring is detected by image analysis, the rotation of the brush 5103 can be stopped.
- the display 5101 can display the remaining battery level, the amount of sucked dust, and the like.
- the route traveled by the cleaning robot 5100 may be displayed on the display 5101. Further, the display 5101 may be a touch panel, and the operation buttons 5104 may be provided on the display 5101.
- the cleaning robot 5100 can communicate with the portable electronic device 5140.
- the image taken by the camera 5102 can be displayed on the portable electronic device 5140. Therefore, the owner of the cleaning robot 5100 can know the state of the room even when he / she is out. Further, the display of the display 5101 can be confirmed by the portable electronic device 5140.
- the light emitting device of one aspect of the present invention can be used for the display 5101.
- the robot 2100 shown in FIG. 8B includes a computing device 2110, an illuminance sensor 2101, a microphone 2102, an upper camera 2103, a speaker 2104, a display 2105, a lower camera 2106, an obstacle sensor 2107, and a moving mechanism 2108.
- the microphone 2102 has a function of detecting a user's voice, environmental sound, and the like. Further, the speaker 2104 has a function of emitting sound.
- the robot 2100 can communicate with the user by using the microphone 2102 and the speaker 2104.
- the display 2105 has a function of displaying various information.
- the robot 2100 can display the information desired by the user on the display 2105.
- the display 2105 may be equipped with a touch panel. Further, the display 2105 may be a removable information terminal, and by installing the display 2105 at a fixed position of the robot 2100, charging and data transfer are possible.
- the upper camera 2103 and the lower camera 2106 have a function of photographing the surroundings of the robot 2100. Further, the obstacle sensor 2107 can detect the presence or absence of an obstacle in the traveling direction when the robot 2100 moves forward by using the moving mechanism 2108. The robot 2100 can recognize the surrounding environment and move safely by using the upper camera 2103, the lower camera 2106, and the obstacle sensor 2107.
- the light emitting device of one aspect of the present invention can be used for the display 2105.
- FIG. 8C is a diagram showing an example of a goggle type display.
- the goggle type display includes, for example, a housing 5000, a display unit 5001, a speaker 5003, an LED lamp 5004, a connection terminal 5006, and a sensor 5007 (force, displacement, position, speed, acceleration, angular speed, rotation speed, distance, light, liquid, etc. Includes functions to measure magnetism, temperature, chemicals, voice, time, hardness, electric field, current, voltage, power, radiation, flow rate, humidity, gradient, vibration, odor, or infrared rays), microphone 5008, display 5002 , Support portion 5012, earphone 5013, etc.
- the light emitting device of one aspect of the present invention can be used for the display unit 5001 and the display unit 5002.
- FIG. 9 is an example in which the light emitting device according to the second embodiment is used for a desk lamp which is a lighting device.
- the desk lamp shown in FIG. 9 has a housing 2001 and a light source 2002, and the lighting device according to the third embodiment may be used as the light source 2002.
- FIG. 10 is an example in which the light emitting device according to the second embodiment is used as an indoor lighting device 3001. Since the light emitting device according to the second embodiment is a light emitting device having high luminous efficiency, it can be a lighting device having low power consumption. Further, since the light emitting device according to the second embodiment can have a large area, it can be used as a lighting device having a large area. Further, since the light emitting device according to the second embodiment is thin, it can be used as a thin lighting device.
- the light emitting device according to the second embodiment can also be mounted on the windshield or dashboard of an automobile.
- FIG. 11 shows an aspect in which the light emitting device according to the second embodiment is used for a windshield or a dashboard of an automobile.
- the display area 5200 to the display area 5203 are display areas provided by using the light emitting device according to the second embodiment.
- the display area 5200 and the display area 5201 are display devices equipped with the light emitting device according to the second embodiment provided on the windshield of the automobile.
- the light emitting device according to the second embodiment can be a so-called see-through display device in which the opposite side can be seen through by manufacturing the first electrode and the second electrode with electrodes having translucency. .. If the display is in a see-through state, even if it is installed on the windshield of an automobile, it can be installed without obstructing the view.
- a transistor for driving it is preferable to use a transistor having translucency represented by an organic transistor made of an organic semiconductor material and a transistor using an oxide semiconductor.
- the display area 5202 is a display device provided with the light emitting device according to the second embodiment provided in the pillar portion. By projecting an image from an image pickup means provided on the vehicle body on the display area 5202, the view blocked by the pillars can be complemented.
- the display area 5203 provided in the dashboard portion compensates for blind spots and enhances safety by projecting an image from an imaging means provided on the outside of the automobile in a field of view blocked by the vehicle body. Can be done. By projecting the image so as to complement the invisible part, it is possible to confirm the safety more naturally and without discomfort.
- the display area 5203 can also provide various information such as navigation information, speed, revs, mileage, fuel level, gear status, or air conditioning settings.
- the display items, layout, and the like can be appropriately changed according to the user's preference. It should be noted that these information can also be provided in the display area 5200 to the display area 5202. Further, the display area 5200 to the display area 5203 can also be used as a lighting device.
- FIGS. 12A and 12B show a foldable mobile information terminal 5150.
- the foldable portable information terminal 5150 has a housing 5151, a display area 5152, and a bent portion 5153.
- FIG. 12A shows a mobile information terminal 5150 in an expanded state.
- FIG. 12B shows a mobile information terminal in a folded state.
- the portable information terminal 5150 has a large display area 5152, it is compact and excellent in portability when folded.
- the display area 5152 can be folded in half by the bent portion 5153.
- the bent portion 5153 is composed of a stretchable member and a plurality of support members. When folded, the stretchable member is stretched, and the bent portion 5153 is folded with a radius of curvature of 2 mm or more, preferably 3 mm or more. Is done.
- the display area 5152 may be a touch panel (input / output device) equipped with a touch sensor (input device).
- the light emitting device of one aspect of the present invention can be used for the display area 5152.
- FIGS. 13A to 13C show a foldable mobile information terminal 9310.
- FIG. 13A shows a mobile information terminal 9310 in an expanded state.
- FIG. 13B shows a mobile information terminal 9310 in a state of being changed from one of the expanded state or the folded state to the other.
- FIG. 13C shows a mobile information terminal 9310 in a folded state.
- the mobile information terminal 9310 is excellent in portability in the folded state, and is excellent in the listability of the display due to the wide seamless display area in the unfolded state.
- the display panel 9311 is supported by three housings 9315 connected by a hinge 9313.
- the display panel 9311 may be a touch panel (input / output device) equipped with a touch sensor (input device). Further, the display panel 9311 can be reversibly deformed from the unfolded state to the folded state of the portable information terminal 9310 by bending between the two housings 9315 via the hinge 9313.
- the light emitting device of one aspect of the present invention can be used for the display panel 9311.
- the configurations shown in the present embodiment can be used by appropriately combining the configurations shown in the first to fourth embodiments.
- the compound of one aspect of the present invention can be used for a photoelectric conversion element such as an organic thin film solar cell (OPV) or an organic light diode (OPD). More specifically, since it has carrier transportability, it can be used for a carrier transport layer and a carrier injection layer. Further, by using a mixed film with a donor substance, it can be used as a charge generation layer. Further, since it is photoexcited, it can be used as a power generation layer or an active layer.
- a photoelectric conversion element such as an organic thin film solar cell (OPV) or an organic light diode (OPD). More specifically, since it has carrier transportability, it can be used for a carrier transport layer and a carrier injection layer. Further, by using a mixed film with a donor substance, it can be used as a charge generation layer. Further, since it is photoexcited, it can be used as a power generation layer or an active layer.
- OCV organic thin film solar cell
- OPD organic light diode
- the range of application of the light emitting device provided with the light emitting device according to the second embodiment is extremely wide, and this light emitting device can be applied to electronic devices in all fields.
- an electronic device having low power consumption can be obtained.
- the absorption spectrum and the emission spectrum of the toluene solution of DBTPIPt-II are shown in FIG. Further, the absorption spectrum and the emission spectrum of the thin film are shown in FIG.
- the solid thin film was prepared on a quartz substrate by a vacuum vapor deposition method.
- An ultraviolet-visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used for the measurement of the absorption spectrum.
- the absorption spectrum in the solution state was obtained by subtracting the absorption spectrum measured by putting only the solvent in the quartz cell from the absorption spectrum measured by putting the solution of DBTPIPt-II in the quartz cell.
- the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of the quartz substrate from the absorption spectrum of DBTPIPt-II formed on the quartz substrate.
- a fluorometer (FS920 manufactured by Hamamatsu Photonics Co., Ltd.) was used for the measurement of the emission spectrum.
- the DBTPIPt-II thin film has a good film quality with little change and is difficult to aggregate even in the atmosphere.
- An electrochemical analyzer (manufactured by BAS Co., Ltd., model number: ALS model 600A or 600C) was used as the measuring device.
- the solution used for CV measurement was dehydrated dimethylformamide (DMF) (manufactured by Aldrich Co., Ltd., 99.8%, catalog number; 22705-6) as a solvent, and tetra-perchlorate as a supporting electrolyte.
- Dissolve n-butylammonium (n-Bu 4 NCLo 4 ) (manufactured by Tokyo Kasei Co., Ltd., catalog number; T0836) to a concentration of 100 mmol / L, and further measure the object to be measured at a concentration of 2 mmol / L.
- the working electrode is a platinum electrode (PTE platinum electrode manufactured by BAS Co., Ltd.), and the auxiliary electrode is a platinum electrode (BAS Co., Ltd., Pt counter electrode for VC-3). 5 cm))) was used as a reference electrode, and an Ag / Ag + electrode (RE7 non-aqueous solvent system reference electrode manufactured by BAS Co., Ltd.) was used.
- the measurement was performed at room temperature (20 or more and 25 ° C. or less).
- the scan speed at the time of CV measurement was unified to 0.1 V / sec, and the oxidation potential Ea [V] and the reduction potential Ec [V] with respect to the reference electrode were measured.
- Ea was the intermediate potential of the oxidation-reduction wave
- Ec was the intermediate potential of the reduction-oxidation wave.
- the potential energy of the reference electrode used in this embodiment with respect to the vacuum level is known to be -4.94 [eV]
- the HOMO level [eV] -4.94-Ea, LUMO.
- the CV measurement was repeated 100 times, and the oxidation-reduction wave in the measurement at the 100th cycle was compared with the oxidation-reduction wave in the first cycle to examine the electrical stability of the compound.
- a white powder of interest was obtained with a yield of 0.86 g and a yield of 69%.
- 0.85 g of the obtained white powder was sublimated and purified by a train sublimation method under the conditions of a pressure of 3.0 Pa, an argon flow rate of 5.0 mL / min and 260 ° C. for 16 hours. After sublimation purification, 0.77 g of a white solid was obtained with a recovery rate of 91%.
- the synthesis scheme of step 1 is shown below.
- the solid thin film was prepared on a quartz substrate by a vacuum vapor deposition method.
- An ultraviolet-visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used for the measurement of the absorption spectrum.
- the absorption spectrum in the solution state was obtained by subtracting the absorption spectrum measured by putting only the solvent in the quartz cell from the absorption spectrum measured by putting the solution of CzPIPt in the quartz cell.
- the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of the quartz substrate from the absorption spectrum of CzPIPt formed on the quartz substrate.
- a fluorometer (FS920 manufactured by Hamamatsu Photonics Co., Ltd.) was used for the measurement of the emission spectrum.
- the toluene solution of CzPIPt showed an absorption peak in the vicinity of 340 nm, 327 nm, and 294 nm, and the peak of the emission wavelength was 416 nm (excitation wavelength 342 nm). Further, from FIG. 19, the thin film of CzPIPt showed an absorption peak in the vicinity of 344 nm, 331 nm, and 297 nm, and the peak of the emission wavelength was in the vicinity of 425 nm (excitation wavelength 343 nm).
- CzPIPt which is an organic compound according to one aspect of the present invention, can be effectively used as a host transport material for a luminescent substance and a fluorescent luminescent substance in the visible range.
- the mixture was stirred at 180 ° C. for 17 hours under a nitrogen stream. After stirring, the mixture was cooled to room temperature and chloroform was added. The mixture was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the organic layer was dried over magnesium sulfate. The mixture was naturally filtered and the filtrate was concentrated to give an oil.
- step 1 The synthesis scheme of step 1 is shown below.
- the solid thin film was prepared on a quartz substrate by a vacuum vapor deposition method.
- An ultraviolet-visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used for the measurement of the absorption spectrum.
- the absorption spectrum in the solution state was obtained by subtracting the absorption spectrum measured by putting only the solvent in the quartz cell from the absorption spectrum measured by putting the solution of mDPhATPt in the quartz cell.
- the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of the quartz substrate from the absorption spectrum of mDPhATPt formed on the quartz substrate.
- a fluorometer (FS920 manufactured by Hamamatsu Photonics Co., Ltd.) was used for the measurement of the emission spectrum.
- the toluene solution of mDPhATPt showed absorption peaks in the vicinity of 301 nm and 282 nm, and the peak of the emission wavelength was in the vicinity of 415 nm (excitation wavelength 306 nm). Further, from FIG. 22, in the thin film of mDPhATPt, absorption peaks were observed in the vicinity of 304 nm, 281 nm and 258 nm, and the peak of the emission wavelength was observed in the vicinity of 418 nm (excitation wavelength 307 nm). As a result, it was found that mDPhATPt, which is an organic compound according to one aspect of the present invention, can be effectively used as a host transport material for a luminescent substance and a fluorescent luminescent substance in the visible range.
- the mDPhATPt thin film has a good film quality that does not easily aggregate even in the atmosphere and has a small change in morphology.
- HOMO and LUMO levels of mDPhATPt were calculated based on cyclic voltammetry (CV) measurements. Since the calculation method has been described in Synthesis Example 1, repeated description is omitted.
- the light emitting device 1 of one aspect of the present invention and the comparative light emitting device 1 which is a comparative example will be described.
- the structural formulas of the organic compounds used in this example are shown below.
- indium tin oxide (ITSO) containing silicon oxide was formed on a glass substrate by a sputtering method to form a first electrode 101.
- the film thickness was 110 nm, and the electrode area was 2 mm ⁇ 2 mm.
- the surface of the substrate was washed with water, fired at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
- the substrate was introduced into a vacuum vapor deposition apparatus whose internal pressure was reduced to about 1 ⁇ 10 -4 Pa, and the substrate was vacuum fired at 170 ° C. for 30 minutes in a heating chamber inside the vacuum vapor deposition apparatus for 30 minutes. It was allowed to cool to some extent.
- the substrate on which the first electrode 101 is formed is fixed to a substrate holder provided in the vacuum vapor deposition apparatus so that the surface on which the first electrode 101 is formed faces downward, and the first electrode 101 is formed.
- the weight of 4,4'-di (carbazol-9-yl) biphenyl (abbreviation: CBP) and molybdenum oxide represented by the above structural formula (i) by a thin-film deposition method using resistance heating is added.
- mCP 1,3-bis (carbazol-9-yl) benzene represented by the above structural formula (ii) is deposited on the hole injection layer 111 so as to have a film thickness of 20 nm.
- the hole transport layer 112 was formed.
- CzPIPt 3- [4- (carbazole-9-yl) phenyl] imidazole [1,2-f] phenanthridine (abbreviation: CzPIPt) and [Ir (iPrFptz) 3 ] represented by the above structural formula (iv).
- Is co-deposited at 20 nm so as to have a weight ratio of 1: 0.08 ( CzPIPt: [Ir (iPrFptz) 3 ]) to form a second light emitting layer, which is further represented by the above structural formula (v).
- basophenanthroline (abbreviation: Bphen) represented by the above structural formula (vi) was vapor-deposited on the light emitting layer 113 so as to have a film thickness of 15 nm to form an electron transport layer 114.
- lithium fluoride (LiF) is deposited by 1 nm to form an electron injection layer 115, and then aluminum is vapor-deposited to a film thickness of 200 nm to form a second electrode 102. Was formed to produce the light emitting device 1 of this example.
- the light emitting device 2 was manufactured in the same manner as the light emitting device 1 except that the CzPIPt in the light emitting device 1 was changed to DBTPIPt-II.
- Phenanthridine (abbreviation: CzTPt) is changed, and DBTPIPt-II is represented by the above structural formula (viii) 3- [4- (dibenzothiophen-4-yl) phenyl] -1,2,4- It was produced in the same manner as the light emitting device 1 except that it was changed to triazolo [4,3-f] phenanthridine (abbreviation: DBTTPt-II).
- the comparative light emitting device 2 was manufactured in the same manner as the light emitting device 2 except that DBTPIPt-II in the light emitting device 2 was changed to DBTTPt-II.
- the laminated structure of the light emitting device 1, the light emitting device 2, the comparative light emitting device 1 and the comparative light emitting device 2 is summarized in the following table.
- the luminance-current density characteristics of the light emitting device 1, the light emitting device 2, the comparative light emitting device 1 and the comparative light emitting device 2 are shown in FIG. 23, the current efficiency-luminance characteristics are shown in FIG. 24, the brightness-voltage characteristics are shown in FIG. The characteristics are shown in FIG. 26, the external quantum efficiency-luminance characteristics are shown in FIG. 27, and the emission spectrum is shown in FIG. 28.
- Table 2 shows the main characteristics of the light emitting device 1 in the vicinity of 1000 cd / m 2 .
- a color luminance meter (BM-5A, manufactured by Topcon) was used to measure the luminance and CIE chromaticity, and a multi-channel spectroscope (PMA-11, manufactured by Hamamatsu Photonics) was used to measure the emission spectrum. The measurement of each light emitting device was performed at room temperature (atmosphere maintained at 23 ° C.).
- CzPIPt and DBTPIPt-II are organic compounds having a high T1 level that can be used as hosts for blue phosphorescent materials. Further, from FIG. 26, it was found that the light emitting device 1 and the light emitting device 2 of one aspect of the present invention can be driven with a sufficiently low drive voltage.
- FIG. 29 shows the change in the luminance with respect to the driving time under the condition that the initial luminance is 300 cd / m 2 and the current density is constant.
- the light emitting device 1 and the light emitting device 2 which are the light emitting devices of one aspect of the present invention are light emitting devices having a good life.
- the comparative light emitting device 1 which showed good characteristics in the initial characteristics is a light emitting device having a short life and a rapid decrease in brightness.
- the light emitting device 3 of one aspect of the present invention and the comparative light emitting device 3 which is a comparative example will be described.
- the structural formulas of the organic compounds used in this example are shown below.
- indium tin oxide (ITSO) containing silicon oxide was formed on a glass substrate by a sputtering method to form a first electrode 101.
- the film thickness was 110 nm, and the electrode area was 2 mm ⁇ 2 mm.
- the surface of the substrate was washed with water, fired at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
- the substrate was introduced into a vacuum vapor deposition apparatus whose internal pressure was reduced to about 1 ⁇ 10 -4 Pa, and the substrate was vacuum fired at 170 ° C. for 30 minutes in a heating chamber inside the vacuum vapor deposition apparatus for 30 minutes. It was allowed to cool to some extent.
- the substrate on which the first electrode 101 is formed is fixed to a substrate holder provided in the vacuum vapor deposition apparatus so that the surface on which the first electrode 101 is formed faces downward, and the first electrode 101 is formed.
- CBP 4,4'-di (carbazole-9-yl) biphenyl
- molybdenum oxide are added by weight ratio by a vapor deposition method using resistance heating.
- BPAFLP 4-phenyl-4'-(9-phenylfluorene-9-yl) triphenylamine
- the light emitting layer 113 was formed by co-depositing at 30 nm so as to be mDPhATPt: [Ir (ppy) 3 ]).
- lithium fluoride (LiF) is deposited by 1 nm to form an electron injection layer 115, and then aluminum is vapor-deposited to a film thickness of 200 nm to form a second electrode 102. Was formed to produce the light emitting device 3 of this example.
- the laminated structure of the light emitting device 3 and the comparative light emitting device 3 is summarized in the following table.
- the luminance-current density characteristics of the light emitting device 1 and the comparative light emitting device 3 are shown in FIG. 30, the current efficiency-luminance characteristics are shown in FIG. 31, the brightness-voltage characteristics are shown in FIG. 32, the current-voltage characteristics are shown in FIG. 33, and the external quantum efficiency.
- the luminance characteristic is shown in FIG. 34, the luminance-power efficiency characteristic is shown in FIG. 35, and the emission spectrum is shown in FIG. Table 4 shows the main characteristics of the light emitting device 3 and the comparative light emitting device 3 in the vicinity of 1000 cd / m 2 .
- a color luminance meter (BM-5A, manufactured by Topcon) was used to measure the luminance and CIE chromaticity, and a multi-channel spectroscope (PMA-11, manufactured by Hamamatsu Photonics) was used to measure the emission spectrum. The measurement of each light emitting device was performed at room temperature (atmosphere maintained at 23 ° C.).
- the light emitting device 3 and the comparative light emitting device 3 of one aspect of the present invention have obtained light emission derived from [Ir (ppy) 3 ], which is a green phosphorescent dopant. Further, from FIGS. 31, 34, and 35, it was found that the light emitting device 3 of one aspect of the present invention is an EL device having better current efficiency, external quantum efficiency, and power efficiency than the comparative light emitting device 3. Further, from FIG. 33, it was found that the light emitting device 3 of one aspect of the present invention is a light emitting device having a low drive voltage and low power consumption.
- mDPhATPt according to one aspect of the present invention is suitable as a host material for the light emitting layer of the green phosphorescent device. Therefore, mDPhATPt was found to be an organic compound with a high T1 level that can be used as a host for green phosphorescent materials.
- the light emitting device 4 of one aspect of the present invention and the comparative light emitting device 4 which is a comparative example will be described.
- the structural formulas of the organic compounds used in this example are shown below.
- indium tin oxide (ITSO) containing silicon oxide was formed on a glass substrate by a sputtering method to form a first electrode 101.
- the film thickness was 110 nm, and the electrode area was 2 mm ⁇ 2 mm.
- the surface of the substrate was washed with water, fired at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
- the substrate was introduced into a vacuum vapor deposition apparatus whose internal pressure was reduced to about 1 ⁇ 10 -4 Pa, and the substrate was vacuum fired at 170 ° C. for 30 minutes in a heating chamber inside the vacuum vapor deposition apparatus for 30 minutes. It was allowed to cool to some extent.
- the substrate on which the first electrode 101 is formed is fixed to a substrate holder provided in the vacuum vapor deposition apparatus so that the surface on which the first electrode 101 is formed faces downward, and the first electrode 101 is formed.
- BPAFLP 4-phenyl-4'-(9-phenylfluoren-9-yl) triphenylamine
- molybdenum oxide represented by the above structural formula (ix) by a vapor deposition method using resistance heating.
- BPAFLP was deposited on the hole injection layer 111 so as to have a film thickness of 20 nm to form the hole transport layer 112.
- DBTPIPt-II is vapor-filmed on the light emitting layer 113 so as to have a film thickness of 30 nm to form a first electron transport layer, and then basophenanthrolin (abbreviation: Bphen) represented by the above structural formula (vi).
- Bphen basophenanthrolin
- lithium fluoride (LiF) is deposited by 1 nm to form an electron injection layer 115, and then aluminum is vapor-deposited to a film thickness of 200 nm to form a second electrode 102. Was formed to produce the light emitting device 4 of this example.
- the comparative light emitting device 4 is a light emitting device having the same phosphorescent dopant as the light emitting device 4.
- the BPAFLP in the hole injection layer of the light emitting device 4 is converted into 4,4-di (N-carbazolyl) biphenyl (abbreviation: CBP) represented by the above structural formula (i) in the hole transport layer.
- CBP 4,4-di (N-carbazolyl) biphenyl
- BPAFLP is represented by the above structural formula (xiii) in 3,3'-bis (9-phenyl-9H-carbazole) (abbreviation: PCCP)
- DBTPIPt-II in the light emitting layer is represented by the above structural formula (xiv).
- the laminated structure of the light emitting device 4 and the comparative light emitting device 4 is summarized in the following table.
- the luminance-current density characteristics of the light emitting device 4 and the comparative light emitting device 4 are shown in FIG. 37, the current efficiency-luminance characteristics are shown in FIG. 38, the brightness-voltage characteristics are shown in FIG. 39, the current-voltage characteristics are shown in FIG.
- the luminance characteristic is shown in FIG. 41, the luminance-power efficiency characteristic is shown in FIG. 42, and the emission spectrum is shown in FIG. 43.
- Table 6 shows the main characteristics of the light emitting device 4 and the comparative light emitting device 4 in the vicinity of 1000 cd / m 2 .
- a color luminance meter (BM-5A, manufactured by Topcon) was used to measure the luminance and CIE chromaticity, and a multi-channel spectroscope (PMA-11, manufactured by Hamamatsu Photonics) was used to measure the emission spectrum. The measurement of each light emitting device was performed at room temperature (atmosphere maintained at 23 ° C.).
- the light emitting device 4 and the comparative light emitting device 4 of one aspect of the present invention have obtained light emission derived from [Ir (ppy) 3 ], which is a green phosphorescent dopant. Further, from FIGS. 38, 41 and 42, it was found that the light emitting device 4 of one aspect of the present invention is an EL device having better current efficiency, external quantum efficiency and power efficiency than the comparative light emitting device 4. Further, from FIG. 40, it was found that the light emitting device 4 of one aspect of the present invention is a light emitting device having a low drive voltage and low power consumption.
- DBTPIPt-II which is one aspect of the present invention, is suitable as a host material for the light emitting layer of the green phosphorescent device. From this, it was found that DBTPIPt-II is an organic compound having a high T1 level that can be used as a host for the green phosphorescent material. This is more like DBTPIPt-II than a substituent at the 7-position of the 4- (dibenzothiophen-4-yl) phenyl] imidazole [1,2-f] phenanthridine skeleton like 7mDBTPIPt-II.
- DBTPIPt-II is suitable when used as an electron transport layer because it has high electron transport property and can lower the drive voltage.
- the light emitting device 5 of one aspect of the present invention described in the embodiment and the comparative light emitting device 5 which is a comparative example will be described.
- the structural formulas of the organic compounds used in this example are shown below.
- indium tin oxide (ITSO) containing silicon oxide was formed on a glass substrate by a sputtering method to form a first electrode 101.
- the film thickness was 110 nm, and the electrode area was 2 mm ⁇ 2 mm.
- the surface of the substrate was washed with water, fired at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
- the substrate was introduced into a vacuum vapor deposition apparatus whose internal pressure was reduced to about 1 ⁇ 10 -4 Pa, and the substrate was vacuum fired at 170 ° C. for 30 minutes in a heating chamber inside the vacuum vapor deposition apparatus for 30 minutes. It was allowed to cool to some extent.
- the substrate on which the first electrode 101 is formed is fixed to a substrate holder provided in the vacuum vapor deposition apparatus so that the surface on which the first electrode 101 is formed faces downward, and the first electrode 101 is formed.
- BPAFLP 4-phenyl-4'-(9-phenylfluoren-9-yl) triphenylamine
- molybdenum oxide represented by the above structural formula (ix) by a vapor deposition method using resistance heating.
- BPAFLP was deposited on the hole injection layer 111 so as to have a film thickness of 20 nm to form the hole transport layer 112.
- CzPIPt is vapor-filmed on the light emitting layer 113 so as to have a film thickness of 15 nm to form a first electron transport layer, and then basophenanthrolin (abbreviation: Bphen) represented by the above structural formula (vi) is applied.
- Bphen basophenanthrolin
- the electron transport layer 114 was formed by forming a second electron transport layer by vapor deposition so as to have a thickness of 15 nm.
- lithium fluoride (LiF) is deposited by 1 nm to form an electron injection layer 115, and then aluminum is vapor-deposited to a film thickness of 200 nm to form a second electrode 102. Was formed to produce the light emitting device 5 of this example.
- the comparative light emitting device 5 is a light emitting device having the same phosphorescent dopant as the light emitting device 5.
- the BPAFLP in the hole injection layer of the light emitting device 5 is represented by the above structural formula (xvii) of 4,4', 4''- (benzene-1,3,5-triyl) tri (dibenzo).
- BPAFLP used for the hole transport layer and PCBA1BP used for the first light emitting layer are added to thiophene (abbreviation: DBT3P-II) in 3,3'-bis (9) represented by the above structural formula (xiii).
- CzPIPt used for the light emitting layer and the first electron transport layer is represented by the above structural formula (xviii) 2- [3- (carbazole-9).
- -Il) phenyl] imidazo [1,2-f] phenanthridine (abbreviation: 2mCzPIPt) was used for the production.
- the film thickness of the hole injection layer 111 was 60 nm, and the film thickness of the first electron transport layer was 10 nm.
- the materials and film thicknesses of the comparative light emitting device 5 other than the above are the same as those of the light emitting device 5.
- the laminated structure of the light emitting device 5 and the comparative light emitting device 5 is summarized in the following table.
- the luminance-current density characteristics of the light emitting device 5 and the comparative light emitting device 5 are shown in FIG. 44, the current efficiency-luminance characteristics are shown in FIG. 45, the brightness-voltage characteristics are shown in FIG. 46, the current-voltage characteristics are shown in FIG. 47, and the external quantum efficiency.
- the luminance characteristic is shown in FIG. 48, the luminance-power efficiency characteristic is shown in FIG. 49, and the emission spectrum is shown in FIG. Table 8 shows the main characteristics of the light emitting device 5 and the comparative light emitting device 5 in the vicinity of 1000 cd / m 2 .
- a color luminance meter (BM-5A, manufactured by Topcon) was used to measure the luminance and CIE chromaticity, and a multi-channel spectroscope (PMA-11, manufactured by Hamamatsu Photonics) was used to measure the emission spectrum. The measurement of each light emitting device was performed at room temperature (atmosphere maintained at 23 ° C.).
- the light emitting device 5 and the comparative light emitting device 5 of one aspect of the present invention have obtained light emission derived from [Ir (ppy) 3 ], which is a green phosphorescent dopant. From FIGS. 45, 48, and 49, it was found that the light emitting device 5 of one aspect of the present invention is a light emitting device having better current efficiency, external quantum efficiency, and power efficiency than the comparative light emitting device 5. Further, from FIG. 47, it was found that the light emitting device 5 of one aspect of the present invention is a light emitting device having a low drive voltage and low power consumption.
- CzPIPt is suitable as a host material for the light emitting layer of the green phosphorescent device. Therefore, CzPIPt has been found to be an organic compound with a high T1 level that can be used as a host for green phosphorescent materials. This is replaced with a 3-position like CzPIPt rather than a substituent at the 2-position of the 4- (dibenzothiophen-4-yl) phenyl] imidazole [1,2-f] phenanthridine skeleton like 2mCzPIPt. It is suggested that the grouping has a higher T1 level, can excite a shorter wavelength conjugation, and is more efficient. Further, it was found that CzPIPt is suitable when used as a material constituting the electron transport layer because it has high electron transport property and can reduce the driving voltage.
- Electron injection buffer layer 400: Substrate, 401: First electrode, 403: EL layer, 404: Second electrode, 405: Sealing material, 406: Sealing material, 407: Encapsulating substrate, 412: Pad, 420: IC chip, 501: Electrode, 502: Electrode, 511: First light emitting unit, 512: Second light emitting unit, 513: Charge Generation layer, 601: Drive circuit unit (source wire drive circuit), 602: Pixel unit, 603: Drive circuit unit (gate wire drive circuit), 604: Sealing substrate, 605: Sealing material, 607: Space, 608: Wiring , 609: FPC (Flexible Print Circuit),
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Abstract
Description
図2Aおよび図2Bはアクティブマトリクス型発光装置の概念図である。
図3Aおよび図3Bはアクティブマトリクス型発光装置の概念図である。
図4はアクティブマトリクス型発光装置の概念図である。
図5Aおよび図5Bはパッシブマトリクス型発光装置の概念図である。
図6Aおよび図6Bは照明装置を表す図である。
図7A、図7B1、図7B2および図7Cは電子機器を表す図である。
図8A、図8Bおよび図8Cは電子機器を表す図である。
図9は照明装置を表す図である。
図10は照明装置を表す図である。
図11は車載表示装置及び照明装置を表す図である。
図12Aおよび図12Bは電子機器を表す図である。
図13A、図13Bおよび図13Cは電子機器を表す図である。
図14Aおよび図14BはDBTPIPt−IIの1H NMRチャートである。
図15はDBTPIPt−IIのトルエン溶液における吸収スペクトルと発光スペクトルである。
図16はDBTPIPt−IIの薄膜状態における吸収スペクトルと発光スペクトルである。
図17Aおよび図17BはCzPIPtの1H NMRチャートである。
図18はCzPIPtのトルエン溶液における吸収スペクトルと発光スペクトルである。
図19はCzPIPtの薄膜状態における吸収スペクトルと発光スペクトルである。
図20Aおよび図20BはmDPhATPtの1H NMRチャートである。
図21はmDPhATPtのトルエン溶液における吸収スペクトルと発光スペクトルである。
図22はmDPhATPtの薄膜状態における吸収スペクトルと発光スペクトルである。
図23は発光デバイス1、発光デバイス2、比較発光デバイス1および比較発光デバイス2の輝度−電流密度特性である。
図24は発光デバイス1、発光デバイス2、比較発光デバイス1および比較発光デバイス2の電流効率−輝度特性である。
図25は発光デバイス1、発光デバイス2、比較発光デバイス1および比較発光デバイス2の輝度−電圧特性である。
図26は発光デバイス1、発光デバイス2、比較発光デバイス1および比較発光デバイス2の電流−電圧特性である。
図27は発光デバイス1、発光デバイス2、比較発光デバイス1および比較発光デバイス2の外部量子効率−輝度特性である。
図28は発光デバイス1、発光デバイス2、比較発光デバイス1および比較発光デバイス2の発光スペクトルである。
図29は発光デバイス1、発光デバイス2、比較発光デバイス1および比較発光デバイス2の規格化輝度−時間変化特性である。
図30は発光デバイス3および比較発光デバイス3の輝度−電流密度特性である。
図31は発光デバイス3および比較発光デバイス3の電流効率−輝度特性である。
図32は発光デバイス3および比較発光デバイス3の輝度−電圧特性である。
図33は発光デバイス3および比較発光デバイス3の電流−電圧特性である。
図34は発光デバイス3および比較発光デバイス3の外部量子効率−輝度特性である。
図35は発光デバイス3および比較発光デバイス3の輝度−電力効率特性である。
図36は発光デバイス3および比較発光デバイス3の発光スペクトルである。
図37は発光デバイス4および比較発光デバイス4の輝度−電流密度特性である。
図38は発光デバイス4および比較発光デバイス4の電流効率−輝度特性である。
図39は発光デバイス4および比較発光デバイス4の輝度−電圧特性である。
図40は発光デバイス4および比較発光デバイス4の電流−電圧特性である。
図41は発光デバイス4および比較発光デバイス4の外部量子効率−輝度特性である。
図42は発光デバイス4および比較発光デバイス4の輝度−電力効率特性である。
図43は発光デバイス4および比較発光デバイス4の発光スペクトルである。
図44は発光デバイス5および比較発光デバイス5の輝度−電流密度特性である。
図45は発光デバイス5および比較発光デバイス5の電流効率−輝度特性である。
図46は発光デバイス5および比較発光デバイス5の輝度−電圧特性である。
図47は発光デバイス5および比較発光デバイス5の電流−電圧特性である。
図48は発光デバイス5および比較発光デバイス5の外部量子効率−輝度特性である。
図49は発光デバイス5および比較発光デバイス5の輝度−電力効率特性である。
図50は発光デバイス5および比較発光デバイス5の発光スペクトルである。
本実施の形態では、本発明の一態様の有機化合物について説明する。本発明の一態様の有機化合物は、下記一般式(G1)で表される有機化合物である。
本実施の形態では、本発明の一態様の発光デバイスについて説明する。
本実施の形態では、実施の形態2に記載の発光デバイスを用いた発光装置について説明する。
本実施の形態では、実施の形態2に記載の発光デバイスを照明装置として用いる例を図6を参照しながら説明する。図6Bは照明装置の上面図、図6Aは図6Bにおけるe−f断面図である。
本実施の形態では、実施の形態2に記載の発光デバイスをその一部に含む電子機器の例について説明する。実施の形態2に記載の発光デバイスは発光効率が良好であり、消費電力の小さい発光デバイスである。その結果、本実施の形態に記載の電子機器は、消費電力が小さい発光部を有する電子機器とすることが可能である。
本合成例では、実施の形態1において構造式(100)として示した、3−[4−(ジベンゾチオフェン−4−イル)フェニル]イミダゾ[1,2−f]フェナントリジン(略称:DBTPIPt−II)の合成方法について具体的に説明する。DBTPIPt−IIの構造式を下に示す。
200mL三口フラスコに3−ブロモイミダゾ[1,2−f]フェナントリジン0.80g(2.7mmol)、4−(ジベンゾチオフェン−4−イル)フェニルボロン酸1.2g(4.0mmol)、炭酸カリウム1.1g(7.6mmol)、トルエン27mL、エタノール3mL、水3mLを加えた。この混合物を、減圧下で攪拌することで脱気し、フラスコ内を窒素置換した。この混合物に、テトラキス(トリフェニルホスフィン)パラジウム(0)0.12g(0.10mmol)を加え、窒素気流下、80℃で6時間攪拌し、その後、100℃で11時間還流した。還流後、この混合物に水を加え、水層と有機層を分離し、水層をトルエンで抽出した。得られた抽出溶液と有機層を合わせて、飽和炭酸水素ナトリウム水溶液、飽和食塩水で洗浄した後、有機層を硫酸マグネシウムで乾燥した。この混合物を自然濾過して、ろ液を濃縮して油状物を得た。得られた油状物をアルミナカラムクロマトグラフィー(トルエン:酢酸エチル=50:1)で精製し油状物を得た。この油状物に、メタノールを加え超音波を照射し、析出した固体を回収したところ、目的物の白色粉末を収量1.0g、収率79%で得た。得られた白色粉末1.0gをトレインサブリメーション法により圧力3.2Pa、アルゴン流量5.0mL/min、260℃の条件で14時間加熱し、昇華精製した。昇華精製後白色固体を0.89g、回収率87%で得た。ステップ1の合成スキームを下に示す。
本合成例では、実施の形態1において構造式(135)として示した、3−[4−(カルバゾール−9−イル)フェニル]イミダゾ[1,2−f]フェナントリジン(略称:CzPIPt)の合成方法について具体的に説明する。CzPIPtの構造式を下に示す。
200mL三口フラスコに3−ブロモイミダゾ[1,2−f]フェナントリジン0.80g(2.7mmol)、4−(カルバゾール−9−イル)フェニルボロン酸1.3g(4.4mmol)、炭酸カリウム1.0g(7.5mmol)、トルエン30mL、エタノール3mL、水3mLを加えた。この混合物を、減圧下で攪拌することで脱気し、フラスコ内を窒素置換した。この混合物に、テトラキス(トリフェニルホスフィン)パラジウム(0)0.17g(0.15mmol)を加え、窒素気流下、80℃で9時間攪拌した後、100℃で6時間還流した。還流後、この混合物に水を加え、水層と有機層を分離し、水層をトルエンで抽出した。得られた抽出溶液と有機層を合わせて飽和炭酸水素ナトリウム水溶液、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥した。この混合物を自然濾過して、ろ液を濃縮して固体を得た。得られた固体をシリカゲルカラムクロマトグラフィー(トルエン:酢酸エチル=20:1)とアルミナカラムクロマトグラフィー(トルエン:酢酸エチル=50:1)で精製し、固体を得た。この固体をトルエンで再結晶したところ、目的物の白色粉末を収量0.86g、収率69%で得た。得られた白色粉末0.85gをトレインサブリメーション法により圧力3.0Pa、アルゴン流量5.0mL/min、260℃の条件で16時間かけて昇華精製した。昇華精製後白色固体を0.77g、回収率91%で得た。ステップ1の合成スキームを以下に示す。
本合成例では、実施の形態1において構造式(165)として示した3−(1,2,4−トリアゾロ[4,3−f]フェナントリジン−3−イル)トリフェニルアミン(略称:mDPhATPt)の合成方法について具体的に説明する。mDPhATPtの構造式を下に示す。
100mL三口フラスコに3−(3−ブロモフェニル)−1,2,4−トリアゾロ[4,3−f]フェナントリジン1.5g(3.9mmol)、ジフェニルアミン0.67g(4.0mmol)、ヨウ化銅(I)0.14g(0.74mmol)、18−クラウン−6−エーテル0.14g(0.52mmol)、炭酸カリウム1.1g(8.2mmol)、1,3−ジメチル−3,4,5,6−テトラヒドロ−2(1H)−ピリミジノン(略称:DMPU)3mLを加えた。この混合物を、窒素気流下、180℃で17時間攪拌した。攪拌後、この混合物を室温まで降温し、クロロホルムを加えた。この混合物を水、飽和炭酸水素ナトリウム水溶液、飽和食塩水で洗浄し、有機層を硫酸マグネシウムで乾燥した。この混合物を自然濾過し、濾液を濃縮して油状物を得た。得られた油状物をシリカゲルカラムクロマトグラフィー(トルエン:酢酸エチル=10:1)で精製した。この固体にメタノールを加えて超音波を照射し、固体を回収した。得られた固体をトルエンで再結晶したところ、目的物の淡黄色粉末を収量0.79g、収率43%で得た。
まず、ガラス基板上に、酸化珪素を含むインジウム錫酸化物(ITSO)をスパッタリング法にて成膜し、第1の電極101を形成した。なお、その膜厚は110nmとし、電極面積は2mm×2mmとした。
発光デバイス2は、発光デバイス1におけるCzPIPtをDBTPIPt−IIに変えた他は発光デバイス1と同様に作製した。
比較発光デバイス1は、発光デバイス1におけるCzPIPtを上記構造式(vii)で表される3−[4−(9H−カルバゾール−9−イル)フェニル]−1,2,4−トリアゾロ[4,3−f]フェナントリジン(略称:CzTPt)に変え、DBTPIPt−IIを上記構造式(viii)で表される3−[4−(ジベンゾチオフェン−4−イル)フェニル]−1,2,4−トリアゾロ[4,3−f]フェナントリジン(略称:DBTTPt−II)に変えた他は発光デバイス1と同様に作製した。
比較発光デバイス2は発光デバイス2におけるDBTPIPt−IIをDBTTPt−IIに変えた他は発光デバイス2と同様に作製した。
まず、ガラス基板上に、酸化珪素を含むインジウム錫酸化物(ITSO)をスパッタリング法にて成膜し、第1の電極101を形成した。なお、その膜厚は110nmとし、電極面積は2mm×2mmとした。
比較発光デバイス3は、発光デバイス3におけるmDPhATPtを上記構造式(xii)で表される3−[3−(9H−カルバゾール−9−イル)フェニル]−1,2,4−トリアゾロ[4,3−f]フェナントリジン(略称:mCzTPt)に変えた他は発光デバイス3と同様に作製した。
まず、ガラス基板上に、酸化珪素を含むインジウム錫酸化物(ITSO)をスパッタリング法にて成膜し、第1の電極101を形成した。なお、その膜厚は110nmとし、電極面積は2mm×2mmとした。
比較発光デバイス4は、発光デバイス4とりん光ドーパントを同一とした発光デバイスである。比較発光デバイス4は、発光デバイス4の正孔注入層におけるBPAFLPを上記構造式(i)で表される4,4−ジ(N−カルバゾリル)ビフェニル(略称:CBP)に、正孔輸送層におけるBPAFLPを上記構造式(xiii)で表される3,3’−ビス(9−フェニル−9H−カルバゾール)(略称:PCCP)に、発光層におけるDBTPIPt−IIを上記構造式(xiv)で表される7−[3−(ジベンゾチオフェン−4−イル)フェニル]イミダゾ[1,2−f]フェナントリジン(略称:7mDBTPIPt−II)に、電子輸送層におけるDBTPIPt−IIを上記構造式(xv)で表されるN−フェニル−2−[3−(ジベンゾチオフェン−4−イル)フェニル]ベンゾイミダゾール(略称:mDBTBIm−II)に変えて作製した。また、正孔注入層111と、発光層113および第2の電子輸送層の膜厚は各々60nm、40nmおよび20nmとした。比較発光デバイス4における、上記以外の材料および膜厚は発光デバイス4と同一である。
まず、ガラス基板上に、酸化珪素を含むインジウム錫酸化物(ITSO)をスパッタリング法にて成膜し、第1の電極101を形成した。なお、その膜厚は110nmとし、電極面積は2mm×2mmとした。
比較発光デバイス5は、発光デバイス5とりん光ドーパントを同一とした発光デバイスである。比較発光デバイス5は、発光デバイス5の正孔注入層におけるBPAFLPを上記構造式(xvii)で表される4,4’,4’’−(ベンゼン−1,3,5−トリイル)トリ(ジベンゾチオフェン)(略称:DBT3P−II)に、正孔輸送層に用いられたBPAFLPと第1の発光層に用いられたPCBA1BPを上記構造式(xiii)で表される3,3’−ビス(9−フェニル−9H−カルバゾール)(略称:PCCP)に、発光層および第1の電子輸送層に用いられたCzPIPtを上記構造式構造式(xviii)で表される2−[3−(カルバゾール−9−イル)フェニル]イミダゾ[1,2−f]フェナントリジン(略称:2mCzPIPt)に変えて作製した。また、正孔注入層111の膜厚は60nm、第1の電子輸送層の膜厚は10nmとした。比較発光デバイス5における、上記以外の材料および膜厚は発光デバイス5と同一である。
Claims (16)
- 下記一般式(G1)で表される有機化合物。
- 請求項1において、
前記R1乃至R8が水素である有機化合物。 - 請求項2において、
前記R1乃至R16が水素である有機化合物。 - 請求項5において、
前記R1乃至R9およびR20乃至R27が水素である有機化合物。 - 請求項7において、
前記Arが(Ar−1)である有機化合物。 - 請求項1乃至請求項10のいずれか一項に記載の有機化合物を含む発光デバイスのキャリア輸送層用材料。
- 請求項1乃至請求項10のいずれか一項に記載の有機化合物を含む発光デバイスのホスト用材料。
- 陽極と、
陰極と、
前記陽極と前記陰極との間に位置するEL層とを有し、
前記EL層は発光層を有し、
前記発光層は、発光材料と、請求項1乃至請求項10のいずれか一項に記載の有機化合物を有する発光デバイス。 - 請求項13に記載の発光デバイスと、
センサ、操作ボタン、スピーカ、または、マイクとを有する電子機器。 - 請求項13に記載の発光デバイスと、トランジスタ、または、基板とを有する発光装置。
- 請求項13に記載の発光デバイスと、筐体とを有する照明装置。
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