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WO2018186356A1 - Élément électroluminescent organique, dispositif d'éclairage, dispositif d'affichage, et complexe de métal de transition - Google Patents

Élément électroluminescent organique, dispositif d'éclairage, dispositif d'affichage, et complexe de métal de transition Download PDF

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WO2018186356A1
WO2018186356A1 PCT/JP2018/014132 JP2018014132W WO2018186356A1 WO 2018186356 A1 WO2018186356 A1 WO 2018186356A1 JP 2018014132 W JP2018014132 W JP 2018014132W WO 2018186356 A1 WO2018186356 A1 WO 2018186356A1
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group
ring
transition metal
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西関　雅人
山田　哲也
康生 宮田
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Konica Minolta Inc
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/875—Arrangements for extracting light from the devices
    • H10K59/879—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses

Definitions

  • the present invention relates to an organic electroluminescent element, an illumination device, a display device, a transition metal complex, an organic electroluminescent element material, and an organic electroluminescent element material composition, and more particularly, has a sufficiently short-wave emission as a blue phosphorescent element.
  • the present invention relates to an organic electroluminescence element and the like having high luminous efficiency, low driving voltage, and excellent durability.
  • ELD electroluminescence display
  • an inorganic electroluminescence element and an organic electroluminescence element (hereinafter also referred to as an organic EL element) can be given.
  • Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.
  • an organic EL element has a configuration in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, and injects electrons and holes into the light emitting layer to recombine excitons. It is an element that emits light by utilizing the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type complete solid-state device, it is attracting attention from the viewpoints of space saving and portability.
  • Organic EL elements that use phosphorescence emission can in principle achieve light emission efficiency about 4 times that of elements that use previous fluorescence emission. Research and development of electrodes and electrodes are conducted all over the world.
  • the phosphorescence emission method is a method having a very high potential, but in an organic EL device using phosphorescence emission, a method for controlling the position of the emission center, in particular, recombination inside the emission layer, How to stably emit light and how to improve the light emitting property of the phosphorescent material itself is an important technical issue from the viewpoint of the efficiency and life of the device.
  • iridium complexes having ligands such as phenylpyrazole, imidazophenanthridine, and phenylimidazole are known. It is very difficult to satisfy all of light emission and high durability at the same time.
  • a metal complex having phenylimidazole as a ligand is a light emitting material having a relatively short emission wavelength (see, for example, Patent Document 1 and Patent Document 2).
  • the present invention has been made in view of the above-described problems and situations, and the problem to be solved is that the light emission efficiency is high, the driving voltage is low, and the durability is high, while having a sufficiently short-wave emission as a blue phosphorescent element. It is to provide an excellent organic electroluminescence device. Moreover, it is providing the illuminating device and display apparatus with which it was comprised. Furthermore, it is providing the phosphorescence-emitting transition metal complex which can make it possible, the organic electroluminescent element material containing the said phosphorescent metal complex, and organic electroluminescent element material composition.
  • the emission wavelength was shortened by introducing an electron-withdrawing substituent into the phenylimidazole skeleton of a metal complex having phenylimidazole as a ligand, but this emission wavelength was shortened.
  • the light-emitting device is energized even though the light-emitting quantum efficiency (PLQE; light-emitting efficiency by photoexcitation) of the dopant alone measured in a solution state or a solid state is good.
  • PQE light-emitting quantum efficiency by photoexcitation
  • the energy level of the molecular orbital of the metal complex was greatly reduced by the electron-withdrawing group introduced for shortening the wave length, so that the adjacent hole transport layer
  • the level difference between the highest occupied orbital (hereinafter also referred to as HOMO) of the host material in which the metal complex is dispersed in the hole transport material or the light emitting layer and the HOMO level of the metal complex is enlarged.
  • HOMO highest occupied orbital
  • the introduction of the specific hole-transporting substituent disclosed in the present invention promotes hole injection into the light-emitting dopant, and exciton generation due to charge recombination on the metal complex occurs.
  • the light emission efficiency is improved by being promoted, and at the same time, the emission lifetime of the light emitting element can be extended by suppressing the inflow of excessive holes to the adjacent layer of the light emitting layer, which causes a decrease in the light emission lifetime. .
  • the present inventors examined the expansion of applicability of the technical idea of the present invention, and not only a metal complex having phenylimidazole as a ligand, but also a transition having a partial structure represented by the following general formula (2) It has been found that the same effects can be obtained in general metal complexes, and it has been found that the above-mentioned problems can be solved by an organic electroluminescence element containing a phosphorescent transition metal complex represented by the general formula (1).
  • the present inventors have examined the expansion of applicability of the technical idea of the present invention, and are directly bonded to the transition metal as well as the transition metal complex having the partial structure represented by the general formula (2). If the aromatic ring satisfies two specific requirements, the same effect can be obtained for all phosphorescent transition metal complexes consisting of a central metal and a plurality of aromatic ring ligands directly bonded to the central metal. I found out that
  • An organic electroluminescence device containing a phosphorescent transition metal complex in at least one organic layer including a light emitting layer,
  • the transition metal complex has a ligand in which a plurality of aromatic rings are directly bonded to a transition metal as a central metal, and satisfies the following requirements (1) and (2): Electroluminescence element.
  • At least one of the plurality of aromatic rings directly bonded to the transition metal has an electron withdrawing group.
  • At least one of the plurality of aromatic rings directly bonded to the transition metal is a positive chain containing a nitrogen atom and an aromatic ring which are conjugated with the aromatic ring and are connected by a single bond. It has a pore transporting partial structure.
  • any one of the binding orbitals from the highest occupied orbital (HOMO) to the fifth lower energy level (HOMO-5) is the binding orbital.
  • the absolute value of the difference between the energy level of the highest occupied orbital and the binding orbital has an electron density distribution in which 80% or more of the upper electrons exist on the hole transporting partial structure 2.
  • the absolute value of the difference in emission maximum wavelength calculated by molecular orbital calculation for each of the transition metal complex and the transition metal complex having a structure obtained by removing the hole transporting partial structure from the transition metal complex is 10 nm or less. 3.
  • the hole transporting partial structure containing a nitrogen atom and an aromatic ring each may be an unsubstituted or substituted diarylamino group, carbazol-9-yl group, phenoxazin-10-yl group, Item 4.
  • the organic electroluminescence device according to any one of Items 1 to 3, which is selected from a phenothiazin-10-yl group, a dihydrophenazin-5-yl group, and a dihydroacridin-10-yl group. .
  • An organic luminescence device having at least one organic layer including a light emitting layer, wherein at least one of the organic layers contains a transition metal complex represented by the following general formula (1):
  • the organic electroluminescent element according to any one of items 1 to 7.
  • Ring B represents a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle formed with C ⁇ C.
  • Ring C represents a 5- or 6-membered aromatic heterocyclic ring formed with C ⁇ N.
  • Rb and Rc each represents an electron-withdrawing group that can be substituted for ring B and ring C.
  • nb represents an integer of 0 to 3
  • nc represents an integer of 0 to 2. 1 ⁇ nb + nc ⁇ 4.
  • HTG represents a hole transporting partial structure including a nitrogen atom and an aromatic ring.
  • L represents an arylene group having 6 to 10 carbon atoms, and L is bonded to ring B or ring C, but conjugation with ring B or ring C is not continuous.
  • n1 represents 1 or 2.
  • n2 represents 1 or 2.
  • M represents a transition metal of group 8 to 10 in the periodic table.
  • Each of the hole transporting partial structures containing a nitrogen atom and an aromatic ring represented by HTG may be an unsubstituted or substituted diarylamino group, carbazol-9-yl group, phenoxazine- 9.
  • the organic electroluminescence device which is selected from a 10-yl group, a phenothiazin-10-yl group, a dihydrophenazin-5-yl group and a dihydroacridin-10-yl group.
  • the electron-withdrawing group represented by Rb and Rc is selected from a fluorine atom, a cyano group, a carbonyl group, a sulfonyl group, a pentafluorosulfanyl group, an oxycarbonyl group, and a fluorinated alkyl group.
  • Item 11 The organic electroluminescence device according to any one of Items 8 to 10, wherein the aromatic heterocycle represented by the ring C represents an azole ring.
  • Item 12 The organic electroluminescent element according to any one of Items 8 to 11, wherein the aromatic heterocycle represented by the ring C represents an imidazole ring or a triazole ring.
  • Ring A represents a divalent arylene group having 6 to 10 carbon atoms.
  • Ring B represents a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle formed with C ⁇ C.
  • Ring C represents a 5-membered aromatic heterocycle formed with N—C ⁇ N.
  • Ra represents a substitutable substituent.
  • na represents an integer of 0 to 3.
  • Rb and Rc each represents an electron-withdrawing group that can be substituted for ring B and ring C.
  • nb represents an integer of 0 to 3
  • nc represents 0 or 1. 1 ⁇ nb + nc ⁇ 4.
  • Rd and Re each represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
  • nd and ne represent 0 or 1.
  • L 1 , L 2 and L 3 represent a divalent arylene group having 6 to 10 carbon atoms.
  • k represents 0 or 1.
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 represent an aromatic group having 6 to 10 carbon atoms.
  • L 4 , L 5 and L 6 are selected from a single bond, an optionally substituted carbon atom, an optionally substituted nitrogen atom, an oxygen atom and a sulfur atom, and connect adjacent aromatic rings.
  • m, n, and o represent 0 or 1, and when it is 0, the corresponding Lx does not exist, and adjacent aromatic rings are not connected to each other.
  • x represents any of 4, 5 and 6.
  • p, q and r each represents 0 or 1; 1 ⁇ p + q + r ⁇ 2.
  • M represents a transition metal of group 8 to 10 in the periodic table.
  • R 1 and R 2 each represent a hydrogen atom or a substituent, and at least one of R 1 and R 2 represents a substituent.
  • Y 1 and Y 2 represent a carbon atom or a nitrogen atom.
  • Ring C represents a 5-membered aromatic heterocycle formed with N—C ⁇ N.
  • Ra represents a substitutable substituent
  • na represents an integer of 0 to 3.
  • Rb and Rc each represents an electron-withdrawing substituent that can be substituted for ring B and ring C.
  • nb represents an integer of 0 to 3
  • nc represents 0 or 1. 1 ⁇ nb + nc ⁇ 4.
  • Rd and Re each represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
  • L 1 , L 2 and L 3 each represent a divalent arylene group having 6 to 10 carbon atoms.
  • k represents 0 or 1;
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 each represents an aromatic group having 6 to 10 carbon atoms.
  • L 4 , L 5 and L 6 are selected from a single bond, an optionally substituted carbon atom, an optionally substituted nitrogen atom, an oxygen atom and a sulfur atom, and connect adjacent aromatic rings.
  • m, n, and o represent 0 or 1, and when it is 0, the corresponding Lx does not exist, and adjacent aromatic rings are not connected to each other.
  • x represents 4, 5, or 6.
  • X 1 and X 2 represent a carbon atom, and the other represents a nitrogen atom.
  • Y 1 and Y 2 represent a carbon atom or a nitrogen atom.
  • Ra represents a substitutable substituent, and na represents an integer of 0 to 3.
  • Rb and Rc each represents an electron-withdrawing group that can be substituted for ring B and ring C.
  • nb represents an integer of 0 to 3
  • nc represents 0 or 1. 1 ⁇ nb + nc ⁇ 4.
  • Rd and Re each represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
  • L 1 , L 2 and L 3 represent a divalent arylene group having 6 to 10 carbon atoms.
  • k represents 0 or 1.
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 represent an aromatic group having 6 to 10 carbon atoms.
  • L 4 , L 5 and L 6 are selected from a single bond, an optionally substituted carbon atom, an optionally substituted nitrogen atom, an oxygen atom and a sulfur atom, and connect adjacent aromatic rings.
  • m, n, and o represent 0 or 1, and when it is 0, the corresponding Lx does not exist, and adjacent aromatic rings are not connected to each other.
  • x represents 4, 5, or 6.
  • Ra represents a substitutable substituent
  • na represents an integer of 0 to 3.
  • Rb and Rc each represents an electron-withdrawing group that can be substituted for ring B and ring C.
  • nb represents an integer of 0 to 3
  • nc represents 0 or 1. 1 ⁇ nb + nc ⁇ 4.
  • Rd and Re each represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
  • nd and ne represent 0 or 1.
  • L 1 , L 2 and L 3 represent a divalent arylene group having 6 to 10 carbon atoms.
  • k represents 0 or 1.
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 represent an aromatic group having 6 to 10 carbon atoms.
  • L 4 , L 5 , and L 6 are selected from a single bond, an optionally substituted carbon atom, an optionally substituted nitrogen atom, an oxygen atom, and a sulfur atom, and connect adjacent aromatic rings.
  • m, n, and o represent 0 or 1, and when it is 0, the corresponding Lx does not exist, and adjacent aromatic rings are not connected to each other.
  • x represents 4, 5, or 6.
  • R 1 and R 2 each represent a hydrogen atom or a substituent, and at least one of R 1 and R 2 represents a substituent.
  • the organic electroluminescent element according to any one of items 1 to 16.
  • a display device comprising the organic electroluminescence element according to any one of items 1 to 20.
  • An organic electroluminescence device according to any one of items 1 to 20 is provided.
  • a phosphorescent transition metal complex having a ligand in which a plurality of aromatic rings are directly bonded to a transition metal as a central metal characterized by satisfying the following four requirements Complex.
  • At least one of the plurality of aromatic rings directly bonded to the transition metal has an electron withdrawing group.
  • At least one of the plurality of aromatic rings directly bonded to the transition metal is a positive chain containing a nitrogen atom and an aromatic ring which are conjugated with the aromatic ring and are connected by a single bond. It has a hole transporting partial structure.
  • one of the binding orbitals from the highest occupied orbital (HOMO) to the fifth lower energy level (HOMO-5) is an electron on the binding orbital.
  • An organic electroluminescent element material composition comprising the transition metal complex according to item 23.
  • an organic electroluminescence device having high emission efficiency, low driving voltage and excellent durability while having sufficiently short-wave light emission as a blue phosphorescent device.
  • a lighting device and a display device including the same can be provided.
  • the phosphorescent transition metal complex which can make it possible, the organic electroluminescent element material and organic electroluminescent element material composition containing the said phosphorescent metal complex can be provided.
  • the emission wavelength can be shortened.
  • a hole transporting group it is considered that the emission wavelength can be suppressed and the hole injection into the dopant can be promoted. For this reason, it is considered that the light emission efficiency can be improved, the life deterioration due to excessive inflow of holes into the adjacent layer of the light emitting layer, which causes the light emission life to be reduced, can be improved, and the driving voltage can be kept low.
  • Schematic diagram of the display unit of the display device of FIG. 1 is a circuit diagram of a pixel of the display device of FIG.
  • Schematic diagram of a passive matrix display device Schematic of lighting device Cross section of the lighting device
  • the organic electroluminescence device of the present invention is an organic electroluminescence device containing a phosphorescent transition metal complex in at least one organic layer including a light emitting layer, wherein the transition metal complex is a central metal. It has a ligand in which a plurality of aromatic rings are directly bonded to the transition metal, and satisfies the requirements (1) and (2). This feature is a technical feature common to or corresponding to the claimed invention.
  • the transition metal complex has a lower energy level (HOMO-5) lower than the highest occupied orbital (HOMO) in the evaluation by molecular orbital calculation.
  • HOMO-5 lower than the highest occupied orbital (HOMO) in the evaluation by molecular orbital calculation.
  • HOMO highest occupied orbital
  • the absolute value of the difference between the energy level of the orbit and the binding orbit is preferably less than 0.7 eV.
  • the absolute value of the difference in emission maximum wavelength calculated by molecular orbital calculation for each of the transition metal complex and the transition metal complex having a structure obtained by removing the hole transporting partial structure from the transition metal complex is 10 nm. The following is preferable.
  • the hole transporting partial structure containing a nitrogen atom and an aromatic ring may be an unsubstituted or substituted diarylamino group, carbazol-9-yl group, phenoxy group, respectively. It is preferably selected from a sadin-10-yl group, a phenothiazin-10-yl group, a dihydrophenazin-5-yl group and a dihydroacridin-10-yl group.
  • the electron withdrawing group is preferably selected from a fluorine atom, a cyano group, a carbonyl group, a sulfonyl group, a pentafluorosulfanyl group, an oxycarbonyl group, and a fluorinated alkyl group.
  • At least one of the plurality of aromatic rings directly bonded to the transition metal is an azole ring.
  • At least one of the plurality of aromatic rings directly bonded to the transition metal is an imidazole ring or a triazole ring.
  • An embodiment of the present invention is an organic luminescence device having at least one organic layer including a light emitting layer, from the viewpoint of manifesting the effects of the present invention, wherein at least one of the organic layers is represented by the general formula (1). It is preferable to contain the transition metal complex represented by these.
  • the phosphorescent transition metal complex having the partial structure represented by the general formula (2) is easy to synthesize the ligand constituting the transition metal complex. From the viewpoints of the properties and ease of synthesis of the transition metal complex.
  • each of the hole transporting partial structures containing a nitrogen atom and an aromatic ring represented by HTG may be an unsubstituted or substituted diarylamino group, carbazol-9-yl group, phenoxy group. It is preferably selected from a sadin-10-yl group, a phenothiazin-10-yl group, a dihydrophenazin-5-yl group and a dihydroacridin-10-yl group.
  • the electron withdrawing group represented by Rb and Rc is selected from a fluorine atom, a cyano group, a carbonyl group, a sulfonyl group, a pentafluorosulfanyl group, an oxycarbonyl group, and a fluorinated alkyl group. Is preferred.
  • ring C is a 5-membered nitrogen-containing heteroaromatic ring having 3 or less nitrogen atoms from the viewpoint of robustness of the compound. It is preferable. That is, ring C is preferably an azole ring. More preferably, it is an imidazole ring or a triazole ring.
  • the ring C is preferably an azole ring, and more specifically,
  • the phosphorescent transition metal complex represented by the formula (2) is preferably a phosphorescent transition metal complex having a partial structure represented by the general formula (3).
  • the phosphorescent transition metal complex represented by the general formula (1) is a phosphorescent transition metal complex having a partial structure represented by the general formula (3). preferable.
  • the ring B is a 6-membered aromatic from the viewpoint of luminescence and fastness of the compound. It is preferably a hydrocarbon ring or a nitrogen-containing heteroaromatic ring. That is, the phosphorescent transition metal complex having the partial structure represented by the general formula (2) or (3) is the phosphorescent transition metal complex having the partial structure represented by the general formula (4). A metal complex is preferred.
  • the phosphorescent transition metal complex represented by the general formula (1) is a phosphorescent transition metal complex having a partial structure represented by the general formula (4). preferable.
  • the phosphorescent transition metal complex having the partial structure represented by the general formula (4) is phosphorescent having the partial structure represented by either the general formula (5) or (6).
  • a luminescent transition metal complex is preferred.
  • the electron-withdrawing group represented by Rb and Rc is a fluorine atom, a cyano group, a carbonyl group, a sulfonyl group, a pentafluorosulfanyl group, an oxycarbonyl group, or a fluorinated group. It is preferably selected from alkyl groups.
  • the transition metal is preferably iridium.
  • the organic layer containing the phosphorescent transition metal complex is a coating formation layer because a homogeneous film is easily obtained and pinholes are hardly generated.
  • the organic EL element of the present invention can be suitably included in a lighting device and a display device.
  • the transition metal complex of the present invention is a phosphorescent transition metal complex having a ligand in which a plurality of aromatic rings are directly bonded to a transition metal as a central metal, It is preferable to satisfy the four requirements (1) to (4).
  • the phosphorescent transition metal complex of the present invention can be preferably used as a material for an organic electroluminescence element.
  • composition containing the phosphorescent transition metal complex of the present invention can be preferably used as a material composition for an organic electroluminescence device.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the organic electroluminescence device of the present invention is an organic electroluminescence device containing a phosphorescent transition metal complex in at least one organic layer including a light emitting layer, wherein the transition metal complex is a central metal. It has a ligand in which a plurality of aromatic rings are directly bonded to a transition metal, and satisfies the following requirements (1) and (2). (1) At least one of the plurality of aromatic rings directly bonded to the transition metal has an electron withdrawing group. (2) At least one of the plurality of aromatic rings directly bonded to the transition metal is a positive chain containing a nitrogen atom and an aromatic ring which are conjugated with the aromatic ring and are connected by a single bond. It has a hole transporting partial structure.
  • the phosphorescent transition metal complex in the phosphorescent transition metal complex, at least one of a plurality of aromatic rings directly bonded to the transition metal has an electron-withdrawing group, whereby the transition metal The triplet excitation energy of the complex is expanded, and the wavelength of phosphorescence emission accompanying triplet transition is shortened.
  • the energy level of the highest occupied orbital (HOMO) of the transition metal complex is lowered, so that adjacent hole transport is performed.
  • the difference in level between the HOMO level of the host material in which the transition metal complex is dispersed in the hole transport material of the layer and the light emitting layer and the HOMO level of the transition metal complex has expanded.
  • the movement of holes from the hole transport material or the host material is inhibited, and as a result, the generation probability of excitons on the transition metal complex is significantly reduced, which may cause a decrease in luminous efficiency. It becomes a problem.
  • the essential requirement for promoting the movement of holes to the transition metal complex and restoring the light emission efficiency is that at least one of the plurality of aromatic rings directly bonded to the transition metal is the aromatic ring. And having a hole transporting partial structure containing a nitrogen atom and an aromatic ring connected by a single bond.
  • the aromatic In the state where the conjugation with the ring is broken, by connecting to the nitrogen atom by a single bond, we succeeded in minimizing the side effects caused by introducing a hole transporting partial structure.
  • the characteristics common to the transition metal complexes satisfying the constituent requirements of the present invention can be confirmed by molecular orbital calculation.
  • the following common features were confirmed by detailed analysis of the electron orbital of the transition metal complex of the present invention by molecular orbital calculation.
  • the molecular orbital calculation method used was calculated by using Gaussian09, which is molecular orbital calculation software manufactured by Gaussian, USA, and performing structural optimization using B3LYP / LANL2DZ as a keyword.
  • the molecular orbital calculation of the transition metal complex of the present invention is performed and the calculated molecular orbital is examined in detail, from the highest occupied orbital (HOMO) to the fifth lowest energy level (HOMO-5) of the transition metal complex.
  • HOMO highest occupied orbital
  • HOMO-5 the fifth lowest energy level
  • the bonding orbitals there is an orbit having an electron density distribution in which 80% or more of the electrons on the bonding orbitals exist on the hole transporting partial structure, and Looking at the absolute value of the difference between the energy level of the highest occupied orbit (HOMO-x: x is one of 1 to 5), it can be confirmed that both are less than 0.7 eV. It was.
  • transition metal complexes that have a hole transporting partial structure but do not satisfy the constituent requirements of the present invention, they are also the highest occupied orbitals of the transition metal complexes.
  • HOMO The electron density distribution in which at least 60% of the electrons on the bonding orbitals are present on the hole transporting partial structure in any one of the bonding orbitals of the lower energy level. Although there are orbits having the above, they were all 0.9 eV or more in terms of the absolute value of the difference between the energy level of the highest occupied orbit and the binding orbit.
  • the absolute value of the difference between the energy level of the highest occupied orbital and the binding orbital among the binding orbitals of the lower energy level from the highest occupied orbital (HOMO) of the transition metal complex is 0. 80% or more of the electrons in the orbit of less than 0.7 eV are distributed in the hole transporting partial structure, which promotes the movement of holes to the transition metal complex of the present invention and restores the luminous efficiency. Conceivable.
  • triplet excitation energy of the transition metal complex having the structure except for the hole transporting moiety triplet excitation energy (T 1) from the said transition metal complex of a transition metal complex of the present invention (T 1 ) Is calculated by molecular orbital calculation, and the triplet excitation energy (T 1 ) is converted into the emission maximum wavelength ( ⁇ max) and compared, the absolute value of the difference between the emission maximum wavelengths is 10 nm or less.
  • the organic layer refers to a layer containing an organic substance.
  • Hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer constituting organic electroluminescence (hereinafter also referred to as organic EL) provided between the anode and the cathode The constituent layers of the organic EL device of the present invention will be described.
  • this invention although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.
  • Anode / light emitting layer / electron transport layer / cathode ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) anode / hole transport layer / anode buffer layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (vii) anode / anode buffer Layer / hole transport layer / light emitting layer / electron transport layer /
  • an organic compound layer including a light emitting layer excluding an anode and a cathode can be used as one light emitting unit, and a plurality of light emitting units can be stacked.
  • the plurality of stacked light emitting units may have a non-light emitting intermediate layer between the light emitting units, and the intermediate layer may further include a charge generation layer.
  • the organic EL element of the present invention is preferably a white light emitting layer, and is preferably a lighting device using these. Each layer which comprises the organic EL element of this invention is demonstrated.
  • the light emitting layer according to the present invention is a layer that emits light when excitons generated by recombination of electrons and holes injected from the cathode or the electron transport layer or the anode or the hole transport layer are deactivated.
  • the portion to be formed may be in the light emitting layer or at the interface between the light emitting layer and the adjacent layer.
  • the total thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the stability of the emission color against the driving current and preventing the application of a high voltage unnecessary during the light emission, and the film homogeneity. It is preferably adjusted in the range of 2 nm to 5 ⁇ m, more preferably adjusted in the range of 2 to 200 nm, particularly preferably in the range of 5 to 100 nm.
  • a light emitting dopant or a host material (hereinafter also referred to as a host compound) described later is used, for example, a vacuum deposition method, a wet method (also referred to as a wet process, for example, a spin coating method, a casting method, a die coating method, Blade coating method, roll coating method, ink jet method, printing method, spray coating method, curtain coating method, LB method (Langmuir-Blodgett method and the like can be mentioned)) and the like.
  • the light emitting layer is a layer formed through a wet process. By forming the layer by a wet process, damage to the light emitting layer due to heat can be reduced as compared with the vacuum deposition method.
  • the light emitting layer of the organic EL device of the present invention contains a light emitting dopant and a host compound, and at least one light emitting dopant is a phosphorescent transition metal complex represented by the general formula (1). It is preferable that there is a phosphorescent transition metal complex having a partial structure represented by any one of the general formulas (2) to (6).
  • the light-emitting layer according to the present invention may be used in combination with compounds described in the following patent publications.
  • Luminescent dopant As the luminescent dopant, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent dopant, a phosphorescent compound, a phosphorescent compound, or the like) can be used.
  • a fluorescent dopant also referred to as a fluorescent compound
  • a phosphorescent dopant also referred to as a phosphorescent dopant, a phosphorescent compound, a phosphorescent compound, or the like
  • the present inventors have used a phosphorescent transition metal complex represented by the general formula (1) as a phosphorescent dopant, It has been found that a high light emission luminance, a low drive voltage, and a long light emission life can be simultaneously achieved while having a short wavelength, and the present invention has been achieved. Moreover, it turned out that the organic electroluminescent element produced using the phosphorescence dopant of this invention is improved also at the point of temporal stability.
  • M is preferably a group 8-10 transition metal in the periodic table.
  • the emission wavelength of the phosphorescent transition metal complex is adjusted to a desired region. Can be controlled.
  • the phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), although the phosphorescence quantum yield is defined to be a compound of 0.01 or more at 25 ° C., the preferred phosphorescence quantum yield is 0.1 or more.
  • the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.
  • phosphorescent dopants There are two types of emission of phosphorescent dopants in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant. It is an energy transfer type to obtain light emission from a phosphorescent dopant. The other is a carrier trap type in which a phosphorescent dopant serves as a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.
  • a phosphorescent transition metal complex represented by the general formula (1) described below is used as the phosphorescent dopant in the embodiment of the present invention.
  • ring B represents a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle formed with C ⁇ C.
  • Examples of the 6-membered aromatic hydrocarbon ring represented by ring B include a benzene ring.
  • Examples of the 5-membered or 6-membered aromatic heterocycle represented by ring B include oxazole ring, pyridine ring, and pyridazine. Ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, thiadiazole ring, and the like.
  • ring B is a 6-membered aromatic hydrocarbon ring or a nitrogen-containing compound from the viewpoint of luminescence and fastness of the compound. It is preferably a heteroaromatic ring, and more preferably, ring B is a benzene ring, a pyridine ring, or a pyrimidine ring.
  • Ring C represents a 5- or 6-membered aromatic heterocycle formed with C ⁇ N.
  • Examples of the 5-membered aromatic heterocycle represented by ring C include a triazole ring, an imidazole ring, and a tetrazole.
  • Examples of the 6-membered aromatic heterocycle represented by ring C include a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, and a triazine ring.
  • the ring C is preferably a pyridine ring or an azole ring, more preferably An azole ring, more preferably an imidazole ring or a triazole ring.
  • Rb and Rc represent electron-withdrawing substituents that can be substituted for ring B and ring C, respectively.
  • electron withdrawing groups include fluorine atoms, cyano groups, nitro groups, fluorinated alkyl groups such as trifluoromethyl groups, fluorinated aryl groups such as pentafluorophenyl groups, formyl groups, alkylcarbonyl groups, arylcarbonyl Group, carbamoyl group, pentafluorosulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfamoyl group, arylsulfamoyl group, phospheno group, phosphine oxide group, and the like.
  • the electron withdrawing group is preferably selected from a fluorine atom, a cyano group, a carbonyl group, a sulfonyl group, a pentafluorosulfanyl group, an oxycarbonyl group, and a fluorinated alkyl group.
  • Nb represents an integer from 0 to 3
  • nc represents an integer from 0 to 2. 1 ⁇ nb + nc ⁇ 4.
  • HTG represents a hole transporting partial structure containing a nitrogen atom and an aromatic ring.
  • the aromatic ring include a benzene ring, a naphthalene ring, a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.
  • HTG is preferably a structure composed of nitrogen atoms substituted by two aromatic rings, and the two aromatic rings may be bonded to each other to form a cyclic structure.
  • the connecting part of the two aromatic rings may be directly bonded by a single bond or bonded via an atom selected from an optionally substituted carbon atom, an optionally substituted nitrogen atom, an oxygen atom and a sulfur atom. May be.
  • aromatic ring may be substituted, and examples of the substituent include a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 4 carbon atoms. preferable.
  • diarylamino group arylheteroarylamino group, bis (heteroarylamino) group, carbazol-9-yl group, phenoxazin-10-yl group, phenothiazin-10-yl group, 5,10-dihydro
  • diarylamino group arylheteroarylamino group, bis (heteroarylamino) group, carbazol-9-yl group, phenoxazin-10-yl group, phenothiazin-10-yl group, 5,10-dihydro Examples include phenazin-5-yl group and 9,10-dihydroacridin-10-yl group. These groups may be further substituted.
  • * represents a binding site with ring B or ring C, which is a ligand part of the transition metal complex, or with linking group L.
  • L represents an arylene group having 6 to 10 carbon atoms, and L is bonded to ring B or ring C, but conjugation with ring B or ring C is not continuous. In order that conjugation does not continue at the bonding part of L and ring B or ring C, the bonding part of L and ring B or ring C is a single bond, and further, L and ring B or ring sandwich this single bond.
  • the dihedral angle formed by C may be 30 ° or more.
  • a substituent may be introduced on two o-position atoms adjacent to the bonding portion between L and ring B or ring C. The dihedral angle becomes larger as the number of substituents to be introduced increases or becomes bulky.
  • an alkyl group or an alkoxy group is preferable, and an alkyl group is more preferable.
  • Examples of the arylene having 6 to 10 carbon atoms include a phenylene group and a naphthalene group which may be unsubstituted or substituted.
  • a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 4 carbon atoms is preferable.
  • n1 represents 1 or 2.
  • n2 represents 1 or 2. When there are a plurality of L, they may be the same or different.
  • linking group L linking groups LG-1 to LG-12 are shown below.
  • * represents a bonding site with a hole transporting partial structure.
  • # represents a binding site with the ligand portion of the transition metal complex.
  • * represents a bonding site with the hole transporting partial structure HTG.
  • # represents a binding site with ring B or ring C which is a ligand part of the transition metal complex.
  • M represents a transition metal of group 8 to 10 in the periodic table.
  • the group 8-10 transition metal include iridium, rhodium, osmium, ruthenium, palladium, platinum, and the like. Iridium, palladium, and platinum are preferable, and iridium is most preferable.
  • L B and L C represent a monoanionic bidentate ligand coordinated to M.
  • Specific examples of monoanionic bidentate ligands represented by L B and L C include ligands of the following formulas.
  • X represents the atom chosen from a nitrogen atom, an oxygen atom, and a sulfur atom.
  • X A and X B represent a carbon atom or a nitrogen atom.
  • a plurality of X A and X B present in each ligand may be the same or different from each other.
  • R ′, R ′′ and R ′′ ′ each represent a hydrogen atom or a substituent.
  • R ′, R ′′ and R ′′ ′ examples include, for example, an alkyl group, an alkenyl group, an alkynyl group, Aromatic hydrocarbon ring group, cycloalkoxy group, cycloalkylthio group, non-aromatic heterocyclic group, aromatic hydrocarbon group, aromatic heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkoxycarbonyl group , Aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group or heteroarylsulfonyl group, amino group, halogen atom, fluorinated hydrocarbon Group, cyano group, nitro group, hydroxy group, mercapto group, silyl
  • a phosphorescent transition metal complex having a partial structure represented by the general formula (3) According to a preferred embodiment of the phosphorescent transition metal complex represented by the general formula (1) One is a phosphorescent transition metal complex in which the partial structure represented by the general formula (2) is a partial structure represented by the following general formula (3).
  • Ring A represents a divalent arylene group having 6 to 10 carbon atoms.
  • Ring B represents a 6-membered aromatic hydrocarbon ring or 5-membered or 6-membered aromatic heterocycle formed with C ⁇ C.
  • Ring C represents a 5-membered aromatic heterocycle formed with N—C ⁇ N.
  • Ra represents a substitutable substituent, and na represents an integer of 0 to 3.
  • Rb and Rc represent electron-withdrawing substituents that can be substituted for ring B and ring C, respectively.
  • nb represents an integer of 0 to 3
  • nc represents 0 or 1. 1 ⁇ nb + nc ⁇ 4.
  • Rd and Re each represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
  • nd and ne represent 0 or 1.
  • L 1 , L 2 and L 3 represent a divalent arylene group having 6 to 10 carbon atoms.
  • k represents 0 or 1;
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 each represent an aromatic group having 6 to 10 carbon atoms.
  • L 4 , L 5 and L 6 are selected from a single bond, an optionally substituted carbon atom, an optionally substituted nitrogen atom, an oxygen atom and a sulfur atom, and connect adjacent aromatic rings.
  • m, n, and o represent 0 or 1, and when it is 0, the corresponding Lx does not exist, and adjacent aromatic rings are not connected to each other.
  • x represents 4, 5, or 6.
  • p, q and r represent 0 or 1; 1 ⁇ p + q + r ⁇ 2.
  • M represents a transition metal of group 8 to 10 in the periodic table.
  • R 1 and R 2 each represent a hydrogen atom or a substituent, and at least one of R 1 and R 2 represents a substituent.
  • Examples of the substituent represented by Ra and R 1 and R 2 include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group).
  • an alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group).
  • Y 1 and Y 2 represent a carbon atom or a nitrogen atom.
  • Ring C represents a 5-membered aromatic heterocycle formed with N—C ⁇ N.
  • Ra represents a substitutable substituent
  • na represents an integer of 0 to 3.
  • Rb and Rc represent electron-withdrawing substituents that can be substituted for ring B and ring C, respectively.
  • nb represents an integer of 0 to 3
  • nc represents 0 or 1. 1 ⁇ nb + nc ⁇ 4.
  • Rd and Re each represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
  • L 1 , L 2 and L 3 represent a divalent arylene group having 6 to 10 carbon atoms.
  • k represents 0 or 1;
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 each represent an aromatic group having 6 to 10 carbon atoms.
  • L 4 , L 5 and L 6 are selected from a single bond, an optionally substituted carbon atom, an optionally substituted nitrogen atom, an oxygen atom and a sulfur atom, and connect adjacent aromatic rings.
  • m, n, and o represent 0 or 1, and when it is 0, there is no corresponding Lx, and adjacent Ar rings are not connected to each other.
  • x represents any of 4, 5 and 6.
  • R 1 and R 2 each represent a hydrogen atom or a substituent, and at least one of R 1 and R 2 represents a substituent.
  • Phosphorescent transition metal complex having a partial structure represented by general formula (5) Further preferred embodiment of phosphorescent transition metal complex represented by general formula (1) One of them is a phosphorescent transition metal complex in which the partial structure represented by the general formula (2) is a partial structure represented by the following general formula (5).
  • One of X1 and X2 represents a carbon atom and the other represents a nitrogen atom.
  • Y 1 and Y 2 represent a carbon atom or a nitrogen atom.
  • Ra represents a substitutable substituent
  • na represents an integer of 0 to 3.
  • Rb and Rc represent electron-withdrawing substituents that can be substituted for ring B and ring C, respectively.
  • nb represents an integer of 0 to 3
  • nc represents 0 or 1. 1 ⁇ nb + nc ⁇ 4.
  • Rd and Re each represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
  • L 1 , L 2 and L 3 represent a divalent arylene group having 6 to 10 carbon atoms.
  • k represents 0 or 1;
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 each represent an aromatic group having 6 to 10 carbon atoms.
  • L 4 , L 5 , and L 6 are selected from a single bond, an optionally substituted carbon atom, an optionally substituted nitrogen atom, an oxygen atom, and a sulfur atom, and connect adjacent aromatic rings.
  • m, n, and o represent 0 or 1, and when it is 0, the corresponding Lx does not exist, and adjacent aromatic rings are not connected to each other.
  • x represents 4, 5, or 6.
  • R 1 and R 2 each represent a hydrogen atom or a substituent, and at least one of R 1 and R 2 represents a substituent.
  • phosphorescent transition metal complex represented by general formula (1) The other is a phosphorescent transition metal complex in which the partial structure represented by the general formula (2) is a partial structure represented by the following general formula (6).
  • Y 1 and Y 2 represent a carbon atom or a nitrogen atom.
  • Ra represents a substitutable substituent
  • na represents an integer of 0 to 3.
  • Rb and Rc represent electron-withdrawing substituents that can be substituted for ring B and ring C, respectively.
  • nb represents an integer of 0 to 3
  • nc represents 0 or 1. 1 ⁇ nb + nc ⁇ 4.
  • Rd and Re each represent a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
  • nd and ne represent 0 or 1.
  • L 1 , L 2 and L 3 represent a divalent arylene group having 6 to 10 carbon atoms.
  • k represents 0 or 1;
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 each represent an aromatic group having 6 to 10 carbon atoms.
  • L 4 , L 5 and L 6 are selected from a single bond, an optionally substituted carbon atom, an optionally substituted nitrogen atom, an oxygen atom and a sulfur atom, and connect adjacent aromatic rings.
  • m, n, and o represent 0 or 1, and when it is 0, the corresponding Lx does not exist, and adjacent aromatic rings are not connected to each other.
  • x represents 4, 5, or 6.
  • R 1 and R 2 each represent a hydrogen atom or a substituent, and at least one of R 1 and R 2 represents a substituent.
  • the molecular orbital calculation method to be used was calculated by using Gaussian09, a molecular orbital calculation software manufactured by Gaussian, USA, and performing structure optimization using B3LYP / LANL2DZ as a keyword.
  • the compound of Calculation Example 1-b which is a compound obtained by substituting the compound of Calculation Example 1-a with a diphenylamino group as a hole transporting partial structure, is HOMO-3 (fourth binding orbital counting from HOMO).
  • the calculation results show that molecular orbitals corresponding to) are distributed on the hole transport site (HTG).
  • the absolute value of the level difference between this orbital energy level and HOMO (hereinafter also simply referred to as level difference) was 0.23 eV.
  • the triplet excitation energy calculated by calculation of this compound is 435 nm
  • the difference from that of the compound of calculation example 1-a for comparison is 4 nm
  • the compound of Calculation Example 1-a was 465 nm and the compound of Calculation Example 1-b was 465 nm, respectively. It was confirmed that the wavelength change was smaller than the calculation result.
  • the compound of Calculation Example 1-c which is a compound obtained by substituting the compound of Calculation Example 1-a with a carbazol-9-yl group as a hole transporting partial structure, is also represented by HOMO-3 (fourth counting from HOMO). It was shown from the calculation results that molecular orbitals corresponding to (binding orbitals) are distributed on the hole transport site (HTG). The level difference between this orbital level and HOMO was 0.45 eV. In addition, the triplet excitation energy calculated by calculation of this compound is 435 nm, the difference from that of the compound of calculation example 1-a for comparison is 4 nm, and it is estimated from the calculation results that the wavelength change is small. . The results of the molecular calculations are summarized in Table I below.
  • the calculation results show that electrons exist inside the region partitioned by solid lines on each atom.
  • the dot notation and the hatched notation indicate that the phases of the molecular orbitals are different from each other.
  • the compound of Calculation Example 2-b which is a compound obtained by substituting the compound of Calculation Example 2-a with a diphenylamino group as a hole transporting partial structure, is HOMO-3 (fourth binding orbital counting from HOMO).
  • the calculation results show that molecular orbitals corresponding to) are distributed on the hole transport site (HTG).
  • the level difference between this orbital level and HOMO was 0.52 eV.
  • the triplet excitation energy calculated by calculation of this compound is 434 nm, and the difference from that of the compound of calculation example 2-a for comparison is 1 nm, and it is estimated from the calculation results that the wavelength change is small. .
  • the compound of Calculation Example 2-c which is a compound obtained by substituting the compound of Calculation Example 2-a with a carbazol-9-yl group as a hole transporting partial structure, is also represented by HOMO-3 (fourth counting from HOMO). It was shown from the calculation results that molecular orbitals corresponding to (binding orbitals) are distributed on the hole transport site (HTG). The level difference between this orbital level and HOMO was 0.63 eV. Further, the triplet excitation energy calculated by calculation of this compound is 435 nm, the difference from that of the compound of Comparative Example 2-a is 2 nm, and it is estimated from the calculation results that the wavelength change is small. . The results of molecular calculations are summarized in Table II below.
  • the compound of Calculation Example 5-b which is a compound obtained by substituting the compound of Calculation Example 5-a with a diphenylamino group as a hole transporting partial structure, has a strong electron-withdrawing substituent effect, and thus the energy level of the entire complex.
  • the calculation results showed that molecular orbitals corresponding to HOMO (the highest level binding orbitals) were distributed on the hole transport sites (HTG) due to the lowering of the position. From the calculation, molecular orbitals corresponding to HOMO-1 (second bonding orbit counted from HOMO) and HOMO-2 (third bonding orbit counted from HOMO) are also present on the hole transport site (HTG). Distribution was shown from the calculation results.
  • the calculation results show that the orbit showing the electron distribution corresponding to HOMO in a normal transition metal complex (for example, the compound of Calculation Example 5-a) is HOMO-3.
  • the orbital level difference between the calculated HOMO and the normal HOMO-3 orbit was 0.31 eV.
  • the triplet excitation energy calculated by calculation of this compound is 427 nm
  • the difference from that of the compound of calculation example 5-a for comparison is ⁇ 1 nm
  • the compound of Calculation Example 5-c which is a compound obtained by substituting the compound of Calculation Example 5-a with a carbazol-9-yl group as a hole transporting partial structure, is also a complex due to the strong electron-withdrawing substituent.
  • the calculation results show that molecular orbitals corresponding to HOMO (bonding orbitals with the highest energy level) are distributed on the hole transport site (HTG) by lowering the overall level. From the calculation, molecular orbitals corresponding to HOMO-1 (second bonding orbit counted from HOMO) and HOMO-2 (third bonding orbit counted from HOMO) are also present on the hole transport site (HTG). Distribution was shown from the calculation results.
  • the calculation results show that the orbit showing the electron distribution corresponding to HOMO in a normal transition metal complex (for example, the compound of Calculation Example 5-a) is HOMO-3.
  • the level difference between the calculated HOMO and the normal HOMO orbital of HOMO-3 was 0.18 eV.
  • the triplet excitation energy calculated by calculation of this compound is 428 nm
  • the difference from that of the compound of Comparative Example 5-a is 0 nm
  • Table V The results of the molecular calculations are summarized in Table V below.
  • the compound of Calculation Example-Comparison 2-b which is a compound in which the compound of Comparative Example 2-a is substituted with a diphenylamino group as a hole transporting partial structure, is HOMO-3 (fourth counting from HOMO).
  • the calculation results show that molecular orbitals corresponding to the bonding orbitals of (HTG) are distributed on the hole transport site (HTG).
  • the level difference between this orbital level and HOMO is 0.92 eV. It can be seen that the level difference is large compared to the transition metal complex of the present invention.
  • the compound of Calculation Example-Comparison 2-c which is a compound obtained by substituting the compound of Calculation Example-Comparative 2-a with a carbazol-9-yl group as a hole transporting partial structure, is also represented by HOMO-3 (from HOMO).
  • the calculation results show that molecular orbitals corresponding to the fourth bonding orbital are distributed on the hole transport site (HTG), and the level difference between this orbital level and HOMO is 1 It can be seen that the level difference is larger than that of the transition metal complex of the present invention.
  • the phosphorescent transition metal complex has a ligand in which a plurality of aromatic rings are directly bonded to the transition metal as the central metal, and (1) the ligand is bonded directly to the transition metal. At least one of the plurality of aromatic rings has an electron-withdrawing group, and (2) at least one of the plurality of aromatic rings directly bonded to the transition metal is bonded to the aromatic ring.
  • the transition metal complex When having a hole transporting partial structure containing a nitrogen atom and an aromatic ring connected to each other by a single bond, the transition metal complex has the highest occupied orbital in the evaluation by molecular orbital calculation.
  • One of the bonding orbitals from (HOMO) to the fifth lower energy level (HOMO-5) is such that 80% or more of the electrons on the bonding orbital are on the hole transporting partial structure.
  • the absolute value of the difference in emission maximum wavelength calculated by the molecular orbital calculation for each of the transition metal complex and the transition metal complex having a structure obtained by removing the hole transporting partial structure from the transition metal complex It was found that the thickness was 10 nm or less as a common characteristic.
  • R 1 and R 2 are synonymous with R 1 and R 2 described in the general formulas (3) to (6), and each represents a hydrogen atom or a substituent, and at least one of R 1 and R 2 is Represents a substituent.
  • Q 101 , Q 102 , Q 103 , Q 201 , Q 202 , Q 203 , Q 301 , Q 302 , Q 401 , Q 402 , Q 403 and Q 404 each independently represent a hydrogen atom or a substituent, and are substituted
  • the groups include Ra 1 , Ra 2 , Ra 3 , Rb 1 , Rb 2 , Rb 3 , Rc 1 , Rc 2 , Rd 1 , Rd 2 , Rd 3 and the general formulas (3) to (6).
  • the substituent described in Rd 4 and the hole transporting partial structure according to the present invention are included.
  • At least one of ring B or ring C has an electron withdrawing group. At least one of ring B or ring C is bonded to any one of the hole transporting partial structures HTG-1 to HTG-15. At this time, they may be bonded via any one of the linking groups LG-1 to LG-12.
  • the hole transporting partial structures HTG-1 to HTG-15 and the linking groups LG-1 to LG-12 have the structures described above.
  • the ligands AL-1 to AL-24 in the above compound examples have the following structures.
  • * represents a binding site with a transition metal.
  • this intermediate B-1 was dissolved in 20 times the amount of methylene chloride: acetonitrile mixed solvent (1: 1), and while stirring this solution, 2.0 equivalents of potassium permanganate and the same weight Of K-10 clay, finely crushed in a mortar, was added little by little. After completion of the addition, the mixture was reacted at room temperature for 4 hours to obtain Intermediate C-1.
  • the reaction mixture was diluted with water and ethyl acetate, washed with water three times, dried over magnesium sulfate, and concentrated under reduced pressure.
  • this intermediate C-2 was dissolved in 20 times the amount of toluene, 0.5 equivalent of p-toluenesulfonic acid was added, and the mixture was reacted for 8 hours with heating under reflux.
  • the reaction solution was neutralized with sodium hydroxide, washed with water three times, and concentrated to obtain a crude product of ligand L-2.
  • Ligand L-3 is synthesized from 3-bromobenzonitrile and 2,6-diisopropylaniline via intermediates D-2 and E-2 by the same reaction as intermediates B-2 and C-2 did.
  • the isolation yield of intermediate D-2 was 80%
  • the isolation yield of intermediate E-2 was 76%
  • the isolation yield of ligand L-3 was 70%.
  • the reaction mixture was diluted with water and ethyl acetate, washed with water three times, dried over magnesium sulfate, and concentrated under reduced pressure.
  • Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamines. And dyes having a high fluorescence quantum yield such as laser dyes and the like, and dyes based on dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.
  • the light-emitting dopant according to the present invention may be used in combination with a plurality of types of compounds, a combination of phosphorescent dopants having different structures, a phosphorescent dopant and A combination of fluorescent dopants may also be used.
  • Known phosphorescent dopants and fluorescent dopants can be used.
  • the host material (also referred to as a host compound) is a compound contained in the light emitting layer, the mass ratio in the layer is 20% or more, and at room temperature (25 ° C.).
  • a phosphorescence quantum yield of phosphorescence is defined as a compound having a value of less than 0.1.
  • the phosphorescence quantum yield is preferably less than 0.01.
  • the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
  • the host compound that can be used in the present invention is not particularly limited, and compounds conventionally used in organic EL elements can be used.
  • a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being longer, and has a high Tg (glass transition temperature) is preferable.
  • conventionally known host compounds may be used alone or in combination of two or more.
  • the host compound used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound (polymerizable host compound) having a polymerizable group such as a vinyl group or an epoxy group.
  • a low molecular compound a high molecular compound having a repeating unit
  • a low molecular compound (polymerizable host compound) having a polymerizable group such as a vinyl group or an epoxy group.
  • one or a plurality of such compounds may be used.
  • host compounds include compounds described in the following documents. JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.
  • Injection layer electron injection layer, hole injection layer >> The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer. May be.
  • An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.
  • Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
  • anode buffer layer (hole injection layer) The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like.
  • copper phthalocyanine is used.
  • Representative phthalocyanine buffer layer oxide buffer layer typified by vanadium oxide, amorphous carbon buffer layer, polymer buffer layer using conductive polymer such as polyaniline (emeraldine) or polythiophene, tris (2-phenylpyridine) )
  • Orthometalated complex layers represented by iridium complexes and the like.
  • azatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as the hole injection material.
  • cathode buffer layer (electron injection layer) The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc.
  • Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc.
  • the buffer layer (injection layer) is preferably a very thin film, and the thickness is preferably in the range of 0.1 nm to 5 ⁇ m, although it depends on the material.
  • ⁇ Blocking layer hole blocking layer, electron blocking layer>
  • the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, as described in JP-A Nos. 11-204258 and 11-204359 and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)”. There is a hole blocking layer.
  • the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.
  • the structure of the electron transport layer described later can be used as a hole blocking layer according to the present invention, if necessary.
  • the hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
  • the hole blocking layer contains the carbazole derivative, carboline derivative, or diazacarbazole derivative (shown in which any one of the carbon atoms constituting the carboline ring of the carboline derivative is replaced by a nitrogen atom). It is preferable to contain.
  • the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers.
  • 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.
  • the ionization potential is defined by the energy required to discharge electrons in the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be determined by the following method, for example.
  • the ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy.
  • a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be suitably used.
  • the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.
  • the structure of the hole transport layer described later can be used as an electron blocking layer as necessary.
  • the thickness of the hole blocking layer and the electron transporting layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
  • the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • azatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as a hole transport material.
  • the above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminoph
  • No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.
  • NPD 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
  • cyclometalated complexes and orthometalated complexes such as copper phthalocyanine and tris (2-phenylpyridine) iridium complex can also be used as the hole transport material.
  • JP-A-11-251067 J. Org. Huang et. al.
  • a so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used.
  • these materials are preferably used because a light-emitting element with higher efficiency can be obtained.
  • the hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can.
  • the thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • This hole transport layer may have a single layer structure composed of one or more of the above materials.
  • a hole transport layer having a high p property doped with impurities examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
  • a hole transport layer having such a high p property because a device with lower power consumption can be produced.
  • the electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
  • the electron transport layer can be provided as a single layer or a plurality of layers.
  • an electron transport material also serving as a hole blocking material used for the electron transport layer adjacent to the cathode side with respect to the light emitting layer was injected from the cathode.
  • Any material can be used as long as it has a function of transferring electrons to the light-emitting layer, and any material known in the art can be selected and used alone or in combination.
  • a nitro-substituted fluorene derivative Diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq 3 ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.
  • metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
  • the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
  • the electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials.
  • an electron transport layer having a high n property doped with impurities examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
  • an electron transport layer having such a high n property because an element with lower power consumption can be produced.
  • anode As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern of a desired shape may be formed by a photolithography method, or when pattern accuracy is not so required (about 100 ⁇ m or more)
  • a pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • wet film-forming methods such as a printing system and a coating system, can also be used.
  • the transmittance be greater than 10%
  • the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.
  • a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.
  • a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic, etc., and it is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic, polyarylate, Arton (trade name, manufactured by JSR) or Appel (
  • the surface of the resin film may be formed with an inorganic film, an organic film, or a hybrid film of both, and the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992.
  • Relative humidity (90 ⁇ 2)% RH) is preferably 0.01 g / (m 2 ⁇ 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987.
  • a high barrier film having a permeability of 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less and a water vapor permeability of 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferable. .
  • the material for forming the barrier film may be any material that has a function of suppressing the intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the method for forming the barrier film is not particularly limited.
  • the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque support substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • the external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.
  • the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element ⁇ 100.
  • a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
  • the ⁇ max of light emission of the organic EL element is preferably 480 nm or less.
  • ⁇ Sealing> As a sealing means used for this invention, the method of adhere
  • the sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. Further, transparency and electrical insulation are not particularly limited.
  • Specific examples include a glass plate, a polymer plate / film, and a metal plate / film.
  • the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the element can be thinned.
  • the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured in (1) is 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesively cured from room temperature to 80 ° C. is preferable.
  • a desiccant may be dispersed in the adhesive.
  • Application of the adhesive to the sealing portion may be performed using a commercially available dispenser or may be printed like screen printing.
  • the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film.
  • the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
  • vacuum deposition sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma
  • a polymerization method a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil
  • a vacuum is also possible.
  • a hygroscopic compound can also be enclosed inside.
  • hygroscopic compound examples include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
  • metal oxides for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
  • sulfates for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate.
  • metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.
  • perchloric acids eg perchloric acid Barium, magnesium perchlorate, and the like
  • anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or the sealing film.
  • the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate.
  • the same glass plate, polymer plate / film, metal plate / film, and the like used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
  • the organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle ⁇ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light undergoes total reflection between the light and the light, and the light is guided through the transparent electrode or the light emitting layer.
  • a method for improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method for improving efficiency by giving light condensing property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on the side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from the substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No.
  • these methods can be used in combination with the organic EL device of the present invention.
  • a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
  • the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
  • the low refractive index layer examples include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
  • the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low-refractive index layer is reduced when the thickness of the low-refractive index medium is about the wavelength of light and the electromagnetic wave exuded by evanescent enters the substrate.
  • the method of introducing a diffraction grating into an interface that causes total reflection or in any medium is characterized by a high effect of improving light extraction efficiency.
  • This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction.
  • Bragg diffraction such as first-order diffraction and second-order diffraction.
  • light that cannot go out due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode). I want to take it out.
  • the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.
  • the refractive index distribution a two-dimensional distribution
  • the light traveling in all directions is diffracted, and the light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any one of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
  • the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL device of the present invention is processed on the light extraction side of the substrate, for example, so as to provide a microlens array-like structure, or in combination with a so-called condensing sheet, for example, with respect to a specific direction, for example, the device light emitting surface.
  • a specific direction for example, the device light emitting surface.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably 10 ⁇ m to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
  • the condensing sheet it is possible to use, for example, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • BEF brightness enhancement film
  • the shape of the prism sheet for example, the base material may be formed by forming a ⁇ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
  • a light diffusion plate / film may be used in combination with the light collecting sheet.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • an anode is produced by forming a thin film made of a desired electrode material, for example, an anode material on a suitable substrate by a method such as vapor deposition or sputtering so as to have a thickness of 1 ⁇ m or less, preferably 10 to 200 nm.
  • organic compound thin films such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which are organic EL element materials, are formed thereon.
  • each of these layers there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) and the like as described above, but it is easy to obtain a homogeneous film and it is difficult to generate pinholes.
  • film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable in the present invention.
  • the organic layer containing the phosphorescent transition metal complex according to the present invention is preferably formed through a wet process for the above reason.
  • liquid medium for dissolving or dispersing the organic EL material according to the present invention examples include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene.
  • Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
  • a dispersion method it can disperse
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm.
  • a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode.
  • An alternating voltage may be applied.
  • the alternating current waveform to be applied may be arbitrary.
  • the organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
  • lighting devices home lighting, interior lighting
  • clock and liquid crystal backlights billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light
  • the light source of a sensor etc. are mentioned, It is not limited to this, It can use effectively for the use as a backlight of a liquid crystal display device, and an illumination light source especially.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like during film formation, if necessary.
  • patterning only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned.
  • a conventionally known method is used. Can do.
  • the light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total of CS-1000 (manufactured by Konica Minolta Co., Ltd.) is applied to the CIE chromaticity coordinates.
  • the organic EL element of the present invention is a white element
  • the display device of the present invention will be described.
  • the display device of the present invention has the organic EL element.
  • the display device of the present invention may be single color or multicolor, but here, the multicolor display device will be described.
  • a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by a vapor deposition method, a cast method, a spin coat method, an inkjet method, a printing method, or the like.
  • the method is not limited, but is preferably a vapor deposition method, an inkjet method, or a printing method. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.
  • a DC voltage When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
  • the alternating current waveform to be applied may be arbitrary.
  • the multicolor display device can be used as a display device, a display, and various light sources.
  • a display device or display full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
  • Display devices and displays include televisions, personal computers, mobile devices, AV devices, teletext displays, information displays in automobiles, and the like. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
  • Light emitting sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. However, it is not limited to this.
  • FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
  • the display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
  • the control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal.
  • the image information is sequentially emitted to scan the image and display the image information on the display unit A.
  • FIG. 2 is a schematic diagram of the display unit A.
  • the display unit A has a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 on the substrate.
  • the main members of the display unit A will be described below.
  • FIG. 2 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
  • the scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated). Not)
  • the pixel 3 When the scanning signal is applied from the scanning line 5, the pixel 3 receives the image data signal from the data line 6 and emits light according to the received image data.
  • a full color display can be achieved by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 3 is a circuit diagram of the pixel.
  • the pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like.
  • a full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.
  • an image data signal is applied from the control unit B to the drain of the switching transistor 11 via the data line 6.
  • a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5
  • the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.
  • the capacitor 13 is charged according to the potential of the image data signal, and the drive transistor 12 is turned on.
  • the drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10.
  • the power supply line 7 connects the organic EL element 10 to the potential of the image data signal applied to the gate. Current is supplied.
  • the driving of the switching transistor 11 When the scanning signal moves to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, since the capacitor 13 holds the charged potential of the image data signal even when the driving of the switching transistor 11 is turned off, the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues.
  • the driving transistor 12 When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
  • the organic EL element 10 emits light by the switching transistor 11 and the drive transistor 12 that are active elements for the organic EL elements 10 of the plurality of pixels, and the organic EL elements 10 of the plurality of pixels 3 emit light. It is carried out.
  • Such a light emitting method is called an active matrix method.
  • the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good.
  • the potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
  • the present invention not only the active matrix method described above, but also a passive matrix light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned.
  • FIG. 4 is a schematic view of a passive matrix display device.
  • a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
  • the pixel 3 connected to the applied scanning line 5 emits light according to the image data signal.
  • the lighting device of the present invention will be described.
  • the illuminating device of this invention has the said organic EL element.
  • the organic EL element of the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a display device that directly recognizes a still image or a moving image ( It may be used as a display.
  • the drive method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method.
  • the organic EL material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device.
  • a plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.
  • a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed.
  • a mask is provided only at the time of forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and it is only necessary to arrange them separately by coating with the mask. Since other layers are common, patterning of the mask or the like is not necessary.
  • an electrode film can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is also improved. According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.
  • luminescent material used for a light emitting layer For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.
  • CF color filter
  • the white light emitting organic EL element according to the present invention is used as a kind of lamp such as household illumination, interior lighting, and exposure light source as various light emitting light sources and lighting devices in addition to the display device and display. It is also useful for display devices such as backlights for liquid crystal display devices.
  • the non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a 300 ⁇ m thick glass substrate is used as a sealing substrate, and an epoxy photocurable adhesive (LUX The track LC0629B) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured, sealed, and illuminated as shown in FIGS.
  • a device can be formed.
  • FIG. 5 shows a schematic diagram of the lighting device. As shown in FIG. 5, the organic EL element 101 is covered with a glass cover 102.
  • the sealing operation with the glass cover 102 is preferably performed in a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more) without bringing the organic EL element 101 into contact with the atmosphere.
  • FIG. 6 shows a cross-sectional view of the lighting device.
  • the lighting device mainly includes a cathode 105, an organic EL layer 106, and a glass substrate 107 with a transparent electrode, and these members are covered with a glass cover 102.
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • the transition metal complex of the present invention can be preferably used as a material for an organic electroluminescence element in the above-described organic electroluminescence element.
  • the composition containing the phosphorescent transition metal complex of the present invention can be preferably used as a material composition for an organic electroluminescence device.
  • Example 1 ⁇ Vapor deposition type blue light emitting organic EL element> ⁇ Production of Blue Light-Emitting Organic EL Element 1-1 >> After patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ⁇ 100 mm ⁇ 1.1 mm glass substrate was formed as a positive electrode on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate, this transparent ITO electrode was provided. The supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, 200 mg of the host compound (OC-11) is put into another resistance heating boat made of molybdenum, 100 mg of the luminescent dopant (Comparative Compound 1) is put into another resistance heating boat made of molybdenum, and the electron transport material 1 is put into another resistance heating boat made of molybdenum. And 200 mg of the electron transport material 2 was placed in another molybdenum resistance heating boat and attached to a vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing the hole injection material 1 and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole injection layer was provided.
  • the heating boat containing the hole transport material 1 was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole transport layer was provided.
  • the hole transport layer was heated by energizing the heating boat containing the host compound (OC-11) and the light-emitting dopant (Comparative Compound 1) at a deposition rate of 0.2 nm / second and 0.035 nm / second, respectively.
  • a 40 nm-thick luminescent layer was provided by co-evaporation.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the electron transport material 1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.
  • the heating boat containing the electron transport material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further form an electron transport layer having a thickness of 20 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • organic EL element 1-1 lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 1-1 was produced.
  • the organic EL element is abbreviated as EL, for example, the organic EL element 1-1 is denoted as EL1-1.
  • FIG. 5 shows a schematic diagram of the lighting device.
  • the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover 102 is a glove box (purity of 99.999% or more in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere). In a high-purity nitrogen gas atmosphere).
  • FIG. 6 shows a cross-sectional view of the lighting device. Inside the lighting device, a glass substrate 107 with a transparent electrode as an anode, an organic EL layer 106 and a cathode 105 are laminated in this order. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • External extraction quantum efficiency Current that gives each organic EL element room temperature (25 ° C.), initial luminance 2000 cd / m 2 , and 4000 cd / m 2 (shown as luminance A and luminance B in the following tables, respectively).
  • the external extraction quantum efficiency ( ⁇ ) was calculated as an evaluation measure of the light emission efficiency by driving at a constant current and measuring the drive current [mA] immediately after the start of lighting.
  • CS-1000 manufactured by Konica Minolta Co., Ltd. was used for measurement of light emission luminance.
  • the external extraction quantum yields are all expressed as relative values with the organic EL element 1-1 at an initial luminance of 2000 cd / m 2 as a reference (100).
  • Drive voltage ⁇ (drive voltage of each element / drive voltage of the organic EL element 1-1 (initial luminance 2000 cd / m 2 )) ⁇ ⁇ 100 A smaller value indicates a lower drive voltage for comparison.
  • Drive voltage increase rate (%) ⁇ [(Drive voltage after driving 200 hours for each organic EL element / V) ⁇ (Initial drive voltage for each organic EL element / V)] / (Initial drive voltage for each organic EL element) / V) ⁇ ⁇ 100 (4)
  • Half light emission lifetime (25 ° C) The half-light emission lifetime was evaluated according to the measurement method shown below.
  • Each organic EL element is driven at a constant current in a high-temperature bath at 25 ° C. and 70 ° C. with a current that gives an initial luminance of 2000 cd / m 2 , and a time to become 1/2 (1000 cd / m 2 ) of the initial luminance is obtained. This was taken as a measure of half-life.
  • the half-light emission lifetime was expressed as a relative value set with the reference (100) as the half-light emission lifetime of the organic EL device 1-1 obtained at 25 ° C.
  • the initial deterioration was expressed as a relative value set with the reference (100) as the half-light emission lifetime of the organic EL element 1-1.
  • the initial deterioration was calculated based on the following formula.
  • Initial degradation ⁇ (90% arrival time of luminance of organic EL element 1-1 (hr)) / (90% arrival time of each organic EL element (hr)) ⁇ ⁇ 100 That is, the smaller the initial deterioration value is, the smaller the initial deterioration is.
  • the organic EL elements 1-7 to 1-75 of the present invention have higher external extraction quantum efficiency and initial luminance than the comparative organic EL elements 1-1 to 1-6. It can be seen that there is little deterioration, and accordingly, it has a long life at both room temperature and high temperature.
  • the phosphorescent transition metal complex according to the present invention is useful to use as a blue light-emitting dopant in at least improving luminous efficiency, reducing driving voltage, and improving luminous lifetime. Recognize.
  • Example 2 ⁇ Wet process type blue light emitting element> ⁇ Preparation of Blue Light-Emitting Organic EL Element 2-1 >> After patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ⁇ 100 mm ⁇ 1.1 mm glass substrate was formed as a positive electrode on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate, this transparent ITO electrode was provided.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • This substrate was transferred to a nitrogen atmosphere, and a solution obtained by dissolving 50 mg of the hole transport material 3 in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. . Furthermore, after irradiating with ultraviolet light for 180 seconds to perform photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to obtain a second hole transport layer.
  • a thin film was formed on the light emitting layer by spin coating using a solution obtained by dissolving 50 mg of the electron transport material 3 in 10 ml of hexafluoroisopropanol (HFIP) at 1000 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer about 30 nm thick.
  • HFIP hexafluoroisopropanol
  • this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, 0.4 nm of potassium fluoride was deposited as a cathode buffer layer, and further 110 nm of aluminum was deposited. Thus, a cathode was formed to produce an organic EL element 2-1.
  • Example 1 in each evaluation of (1) external extraction quantum efficiency, (2) driving voltage, (4) half-light emission lifetime, and (5) initial deterioration, Example 1 was made with reference to the organic EL element 2-1. The relative value was obtained in the same manner as described above.
  • the organic EL elements 2-7 to 2-75 of the present invention have higher external extraction quantum efficiency and initial luminance degradation than the comparative organic EL elements 2-1 to 2-6. Accordingly, it can be seen that the life is long at both room temperature and high temperature.
  • the organic EL elements 2-7 to 2-75 of the present invention also suppress the increase in driving voltage.
  • the phosphorescent property according to the present invention is used as a blue light emitting dopant in order to improve the light emission efficiency, reduce the driving voltage, and improve the light emission life. It can be seen that it is useful to use a transition metal complex of
  • Example 3 ⁇ Vapor deposition type white light emitting element-1> ⁇ Production of White Light-Emitting Organic EL Element 3-1 >> After patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ⁇ 100 mm ⁇ 1.1 mm glass substrate was formed as a positive electrode on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate, this transparent ITO electrode was provided.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, In another molybdenum resistance heating boat, 200 mg of the host compound (OC-11) is added. In another molybdenum resistance heating boat, 100 mg of the luminescent dopant (Comparative Compound 1) is added.
  • the luminescent dopant (D -6) was put in 100 mg, 200 mg of the electron transport material 1 was put in another resistance heating boat made of molybdenum, and 200 mg of the electron transport material 2 was put in another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing the hole injection material 1 and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole injection layer was provided.
  • the heating boat containing the hole transport material 1 was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole transport layer was provided.
  • the heating boat containing the host compound (OC-11), the luminescent dopant (Comparative Compound 1) and the luminescent dopant (D-6) was energized and heated, and the deposition rate was 0.2 nm / second and 0.022 nm, respectively.
  • a light emitting layer having a thickness of 40 nm was provided by co-evaporation on the hole transport layer at a rate of 0.0010 nm / sec.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the electron transport material 1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.
  • the heating boat containing the electron transport material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further form an electron transport layer having a thickness of 20 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 3-1 was produced.
  • Example 1 in each evaluation of (1) external extraction quantum efficiency, (2) driving voltage, (4) half-light emission lifetime, and (5) initial deterioration, Example 1 was made with reference to the organic EL element 3-1. The relative value was obtained in the same manner as described above.
  • the organic EL devices 3-7 to 3-75 of the present invention have higher external extraction quantum efficiency and initial luminance degradation than the comparative organic EL devices 3-1 to 3-6. Accordingly, it can be seen that the life is long at both room temperature and high temperature.
  • the organic EL elements 3-7 to 3-75 of the present invention also suppress the increase in driving voltage.
  • the invention relates to the present invention as a light emitting dopant in order to improve light emission efficiency, drive voltage, and light emission life. It can be seen that it is useful to use a phosphorescent transition metal complex.
  • Example 4 ⁇ Vapor deposition type white light emitting element-2> ⁇ Preparation of white light emitting element 4-1 >> After patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ⁇ 100 mm ⁇ 1.1 mm glass substrate was formed as a positive electrode on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate, this transparent ITO electrode was provided.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, In another molybdenum resistance heating boat, 200 mg of the host compound (OC-11) is added. In another molybdenum resistance heating boat, 100 mg of the luminescent dopant (Comparative Compound 1) is added.
  • the luminescent dopant (D -3) 100 mg, 100 mg of luminescent dopant (D-6) in another molybdenum resistance heating boat, 200 mg of electron transport material 1 in another molybdenum resistance heating boat, and another molybdenum resistance heating boat 200 mg of the electron transport material 2 was put in and attached to a vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing the hole injection material 1 and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole injection layer was provided.
  • the heating boat containing the hole transport material 1 was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole transport layer was provided.
  • the hole transport layer was heated by energizing the heating boat containing the host compound (OC-11) and the light-emitting dopant (Comparative Compound 1) at a deposition rate of 0.2 nm / second and 0.035 nm / second, respectively.
  • a blue light emitting layer having a thickness of 20 nm was provided by co-evaporation.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the host compound (OC-11), the luminescent dopant (D-3), and the luminescent dopant (D-6) was energized and heated, and the deposition rates were 0.2 nm / second and 0.010 nm, respectively.
  • a yellow light emitting layer having a thickness of 20 nm was provided by co-evaporation on the hole transport layer at a rate of 0.0010 nm / sec.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the electron transport material 1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.
  • the heating boat containing the electron transport material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further form an electron transport layer having a thickness of 20 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 4-1 was produced.
  • Example 1 in each evaluation of (1) external extraction quantum efficiency, (2) drive voltage, (4) half-light emission lifetime, and (5) initial deterioration, Example 1 was made with reference to the organic EL element 4-1. The relative value was obtained in the same manner as described above.
  • the organic EL elements 4-7 to 4-75 of the present invention have higher external extraction quantum efficiency and initial luminance degradation than the comparative organic EL elements 4-1 to 4-6. Accordingly, it can be seen that the life is long at both room temperature and high temperature.
  • the organic EL elements 4-7 to 4-75 of the present invention also suppress the increase in driving voltage.
  • Example 5 ⁇ Vapor deposition type white light emitting element-3> ⁇ Preparation of white light emitting element 5-1 >> After patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ⁇ 100 mm ⁇ 1.1 mm glass substrate was formed as a positive electrode on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate, this transparent ITO electrode was provided.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, 200 mg of host compound 1 (OC-11) is put into another resistance heating boat made of molybdenum, 200 mg of host compound 2 (OC-6) is put into another resistance heating boat made of molybdenum, and the luminescent dopant is put into another resistance heating boat made of molybdenum.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing the hole injection material 1 and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole injection layer was provided.
  • the heating boat containing the hole transport material 1 was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole transport layer was provided.
  • the hole transport layer was heated by energizing the heating boat containing the host compound (OC-11) and the light-emitting dopant (Comparative Compound 1) at a deposition rate of 0.2 nm / second and 0.035 nm / second, respectively.
  • a blue light emitting layer having a thickness of 20 nm was provided by co-evaporation.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the host compound (OC-6), the luminescent dopant (D-3) and the luminescent dopant (D-6) was energized and heated, and the deposition rates were 0.2 nm / second and 0.010 nm, respectively.
  • a yellow light emitting layer having a thickness of 20 nm was provided by co-evaporation on the hole transport layer at a rate of 0.0010 nm / sec.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the electron transport material 1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.
  • the heating boat containing the electron transport material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further form an electron transport layer having a thickness of 20 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 5-1 was produced.
  • Example 1 in each evaluation of (1) external extraction quantum efficiency, (2) driving voltage, (4) half light emission lifetime, and (5) initial deterioration, Example 1 was made with reference to the organic EL element 5-1. The relative value was obtained in the same manner as described above.
  • the organic EL elements 5-7 to 5-75 of the present invention have higher external extraction quantum efficiency and initial luminance degradation than the comparative organic EL elements 5-1 to 5-6. Accordingly, it can be seen that the life is long at both room temperature and high temperature.
  • the organic EL elements 5-7 to 5-75 of the present invention also suppress the increase in driving voltage.
  • Example 6 ⁇ Wet process type white light emitting element-1> ⁇ Production of White Light-Emitting Organic EL Element 6-1 >> After patterning a substrate (NA Techno-Glass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • ITO indium tin oxide
  • the substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of the hole transport material 3 dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. After irradiating with ultraviolet light for 180 seconds to carry out photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.
  • a thin film was formed on the light emitting layer by spin coating using a solution obtained by dissolving 50 mg of the electron transport material 3 in 10 ml of hexafluoroisopropanol (HFIP) at 1000 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer about 30 nm thick.
  • HFIP hexafluoroisopropanol
  • this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, 0.4 nm of potassium fluoride was deposited as a cathode buffer layer, and further 110 nm of aluminum was deposited. Thus, a cathode was formed, and an organic EL element 6-1 was produced.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • Example 1 in each evaluation of (1) external extraction quantum efficiency, (2) driving voltage, (4) half-light emission lifetime, and (5) initial deterioration, Example 1 was performed with reference to the organic EL element 6-1. The relative value was obtained in the same manner as described above.
  • the organic EL elements 6-7 to 6-75 of the present invention have high external extraction quantum efficiency and initial luminance degradation. Accordingly, it can be seen that the life is long at both room temperature and high temperature.
  • Example 7 ⁇ Wet process type white light emitting element-2> ⁇ Production of White Light-Emitting Organic EL Element 7-1 >> After patterning a substrate (NA Techno-Glass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • ITO indium tin oxide
  • the substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of the hole transport material 3 dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. After irradiating with ultraviolet light for 180 seconds to carry out photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.
  • a thin film was formed on this light emitting layer by spin coating under a condition of 1000 rpm and 30 seconds using a solution of 50 mg of electron transport material 4 dissolved in 10 ml of methanol. After irradiating with ultraviolet light for 60 seconds to perform photopolymerization / crosslinking, it was further vacuum-dried at 60 ° C. for 1 hour to obtain an electron transport layer having a thickness of about 30 nm.
  • this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, 0.4 nm of potassium fluoride was deposited as a cathode buffer layer, and further 110 nm of aluminum was deposited. Thus, a cathode was formed, and an organic EL element 7-1 was produced.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • Example 1 in each evaluation of (1) external extraction quantum efficiency, (2) drive voltage, (4) half-light emission lifetime, and (5) initial deterioration, Example 1 was made with reference to the organic EL element 7-1. The relative value was obtained in the same manner as described above.
  • the organic EL elements 7-7 to 7-75 of the present invention have higher external extraction quantum efficiency and initial luminance degradation than the comparative organic EL elements 7-1 to 7-6. Accordingly, it can be seen that the life is long at both room temperature and high temperature.
  • the organic EL elements 7-7 to 7-75 of the present invention also suppress the increase in driving voltage.
  • the organic electroluminescence element of the present invention has a sufficiently short wave emission as a blue phosphorescent element, has high emission efficiency, low driving voltage, and excellent durability, and is used as a display device, display, and various light emission sources. Can be used.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

Un problème devant être résolu par la présente invention est la fourniture, sous la forme d'un élément à phosphorescence bleue, d'un élément électroluminescent organique qui a une efficacité d'émission de lumière élevée, une faible tension de commande, et une excellente durabilité tout en ayant une lumière émise à une longueur d'onde suffisamment courte. En outre, un autre problème devant être résolu par la présente invention est de fournir un dispositif d'éclairage et un dispositif d'affichage équipé de l'élément électroluminescent organique. En outre, un autre problème devant être résolu par la présente invention est de fournir un complexe de métal de transition émettant une lumière phosphorescente qui permet de résoudre les problèmes ci-dessus, un matériau d'élément électroluminescent organique qui contient le complexe métallique électroluminescent phosphorescent, et une composition de matériau d'élément électroluminescent organique. Cet élément électroluminescent organique contient un complexe de métal de transition émettant une lumière phosphorescente dans au moins l'une des couches organiques comprenant une couche électroluminescente. L'élément électroluminescent organique est caractérisé en ce que le complexe de métal de transition comprend un ligand dans lequel une pluralité de cycles aromatiques sont directement liés à un métal de transition servant de métal central, et le ligand satisfait à deux exigences spécifiques.
PCT/JP2018/014132 2017-04-04 2018-04-02 Élément électroluminescent organique, dispositif d'éclairage, dispositif d'affichage, et complexe de métal de transition Ceased WO2018186356A1 (fr)

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Cited By (1)

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JP2024102133A (ja) * 2018-12-28 2024-07-30 株式会社半導体エネルギー研究所 発光素子

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WO2007108327A1 (fr) * 2006-03-17 2007-09-27 Konica Minolta Holdings, Inc. Élément électroluminescent organique, dispositif d'affichage et dispositif d'éclairage
JP2013041990A (ja) * 2011-08-16 2013-02-28 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、表示装置、照明装置
JP2014152151A (ja) * 2013-02-12 2014-08-25 Konica Minolta Inc 有機金属錯体、有機エレクトロルミネッセンス素子材料、有機エレクトロルミネッセンス素子、照明装置及び表示装置
JP5730957B2 (ja) * 2005-05-06 2015-06-10 ユニバーサル ディスプレイ コーポレイション 安定ｏｌｅｄ材料及び改善された安定性を有するデバイス

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WO2007108327A1 (fr) * 2006-03-17 2007-09-27 Konica Minolta Holdings, Inc. Élément électroluminescent organique, dispositif d'affichage et dispositif d'éclairage
JP2013041990A (ja) * 2011-08-16 2013-02-28 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、表示装置、照明装置
JP2014152151A (ja) * 2013-02-12 2014-08-25 Konica Minolta Inc 有機金属錯体、有機エレクトロルミネッセンス素子材料、有機エレクトロルミネッセンス素子、照明装置及び表示装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024102133A (ja) * 2018-12-28 2024-07-30 株式会社半導体エネルギー研究所 発光素子
US12448401B2 (en) 2018-12-28 2025-10-21 Semiconductor Energy Laboratory Co., Ltd. Organic compound, light-emitting device, light-emitting apparatus, electronic device, and lighting device

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