WO2016017741A1 - Élément électroluminescent organique, dispositif d'affichage, dispositif d'éclairage, composé émetteur de lumière fluorescente, et film mince émetteur de lumière - Google Patents

Élément électroluminescent organique, dispositif d'affichage, dispositif d'éclairage, composé émetteur de lumière fluorescente, et film mince émetteur de lumière Download PDF

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WO2016017741A1
WO2016017741A1 PCT/JP2015/071618 JP2015071618W WO2016017741A1 WO 2016017741 A1 WO2016017741 A1 WO 2016017741A1 JP 2015071618 W JP2015071618 W JP 2015071618W WO 2016017741 A1 WO2016017741 A1 WO 2016017741A1
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organic
light
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隆太郎 菅原
康生 宮田
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コニカミノルタ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • 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
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to an organic electroluminescence element, a display device, a lighting device, a fluorescent compound, and a light-emitting thin film.
  • the present invention relates to a light-emitting thin film containing the fluorescent compound, a display device provided with the organic electroluminescence element, and a lighting device.
  • Organic EL elements also referred to as “organic electroluminescent elements” using electroluminescence of organic materials (Electro Luminescence: hereinafter abbreviated as “EL”) have already been put into practical use as a new light emitting system that enables planar light emission.
  • EL Electro Luminescence
  • organic EL emission methods There are two types of organic EL emission methods: “phosphorescence emission” that emits light when returning from the triplet excited state to the ground state and “fluorescence emission” that emits light when returning from the singlet excited state to the ground state.
  • phosphorescence emission that emits light when returning from the triplet excited state to the ground state
  • fluorescence emission that emits light when returning from the singlet excited state to the ground state.
  • TTA triplet excitons
  • TTF triplet excitons
  • the TADF mechanism is a compound having a smaller difference ( ⁇ Est) between the singlet excitation energy level and the triplet excitation energy level ( ⁇ Est (TADF) in FIG. 1) as compared with a normal fluorescent compound. Is smaller than ⁇ Est (F).), A light emission mechanism utilizing a phenomenon in which a reverse intersystem crossing from a triplet exciton to a singlet exciton occurs.
  • Non-Patent Document 8 shows that sila [7] helicene having a structure in which the nitrogen atom of carbazole is replaced with a silicon atom shows a high fluorescence quantum yield. Yes.
  • materials using phosphorus atoms it is known in Non-Patent Document 10 that a compound having a benzo [b] phosphole structure has a high fluorescence quantum yield.
  • heat-activated delayed fluorescence of these compounds has not been reported.
  • Patent Document 2 describes the following compound 1 having a carbazole structure. However, it is described that the fluorescence quantum yield measured in a toluene solution of Compound 1 is as low as 13.0%.
  • the present invention has been made in view of the above problems and situations, and a problem to be solved is to provide an organic electroluminescence device having excellent luminous efficiency. Another object of the present invention is to provide a fluorescent compound used in the organic electroluminescent element, a luminescent thin film containing the fluorescent compound, a display device and an illumination device including the organic electroluminescent element.
  • An organic electroluminescence device having an organic layer including at least one light emitting layer between an anode and a cathode, At least one of the light emitting layers has a structure represented by the following general formula (1), and an absolute value ( ⁇ Est) of an energy difference between the lowest excited singlet level and the lowest triplet excited level is 0.
  • An organic electroluminescence device comprising a ⁇ -conjugated compound having a molecular weight of 0.5 eV or less.
  • X 1 represents Si—R 1 (R 2 ), B—R 3 , O, P— (R 4 ) O, SO, or SO 2 .
  • R 1 to R 4 each independently represents a substituent.
  • C 1 to C 4 each represent a carbon atom.
  • Z1 represents together with C 1 and C 2 and Z2 together with C 3 and C 4 each represents an atomic group necessary for forming an aromatic hydrocarbon ring.
  • R 5 and R 6 each independently represents a substituent.
  • n1 and n2 each independently represents an integer of 1 to 4.
  • the ⁇ -conjugated compound having the structure represented by the general formula (1) has a structure represented by the following general formula (4), any one of items 1 to 5
  • the organic electroluminescent element of description wherein, X 1 represents Si—R 1 (R 2 ), B—R 3 , O, P— (R 4 ) O, SO, or SO 2 .
  • R 1 to R 4 each independently represents a substituent.
  • R 5 and R 6 each independently represents a substituent.
  • R 5 and R 6 are substituted or unsubstituted 9,9-dimethylacridinyl group, phenoxazinyl group, carbazolyl group, 5-phenylindoloindolyl group, or 5-phenylphena
  • the ⁇ -conjugated compounds having the structure represented by the general formula (1) are the following A-1 to A-4, B-1 to B-5, C-1 to C-5, C-18 to C—. 21. Any one of items 1 to 7, characterized by having a structure represented by D-1, D-1 to D-5, E-1 to E-5, or F-1 to F-5
  • the organic electroluminescent element of description is the following A-1 to A-4, B-1 to B-5, C-1 to C-5, C-18 to C—. 21. Any one of items 1 to 7, characterized by having a structure represented by D-1, D-1 to D-5, E-1 to E-5, or F-1 to F-5.
  • the light emitting layer contains the ⁇ -conjugated compound and at least one of a fluorescent light emitting compound and a phosphorescent light emitting compound.
  • the organic electroluminescent element of description is the organic electroluminescent element of description.
  • a display device comprising the organic electroluminescence element according to any one of items 1 to 10.
  • An illuminating device comprising the organic electroluminescence element according to any one of items 1 to 10.
  • a display device comprising a liquid crystal element as the illumination device and display means according to item 12.
  • X 1 represents Si—R 1 (R 2 ), B—R 3 , O, P— (R 4 ) O, SO, or SO 2 .
  • R 1 to R 4 each independently represents a substituent.
  • C 1 to C 4 each represent a carbon atom.
  • Z1 represents together with C 1 and C 2 and Z2 together with C 3 and C 4 each represents an atomic group necessary for forming an aromatic hydrocarbon ring.
  • R 5 and R 6 each independently represents a substituent.
  • n1 and n2 each independently represents an integer of 1 to 4.
  • a luminescent thin film comprising the fluorescent compound according to item 14.
  • an organic electroluminescence device having a high fluorescence quantum yield and excellent luminous efficiency can be provided.
  • the fluorescent compound used for the said organic electroluminescent element, the luminescent thin film containing the said fluorescent compound, the display apparatus provided with the said organic electroluminescent element, and an illuminating device can be provided.
  • the expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows. In the present invention, by using a hetero atom that interacts with the electron orbital of the biaryl structure in the bridge portion, the conjugated system is expanded and a skeleton having high planarity can be formed.
  • the present invention having a structure fixed on a plane can provide a ⁇ -conjugated compound with less non-radiation deactivation. That is, a ⁇ -conjugated compound having a high fluorescence quantum yield can be provided. Moreover, it is guessed that the organic electroluminescent element using the (pi) conjugated compound (fluorescent compound) which has a high fluorescence quantum yield is excellent in luminous efficiency.
  • Schematic diagram showing energy diagrams of normal fluorescent compounds and TADF compounds Schematic of the chemical structure and LUMO orbitals of Borol and Silol Schematic diagram showing an example when the ⁇ -conjugated compound according to the present invention acts as an assist dopant and a host compound, respectively.
  • Schematic diagram showing an example of a display device composed of organic EL elements Schematic diagram of an active matrix display device Schematic showing the pixel circuit
  • Schematic diagram of a passive matrix display device Schematic of lighting device Cross section of the lighting device
  • the organic electroluminescent device of the present invention is an organic electroluminescent device having an organic layer including at least one light emitting layer between an anode and a cathode, wherein at least one layer of the light emitting layer has the general formula (1).
  • ⁇ Est absolute value of an energy difference between the lowest excited singlet level and the lowest triplet excited level of 0.5 eV or less.
  • This feature is a technical feature common to the inventions according to claims 1 to 15.
  • a ⁇ -conjugated compound having a structure represented by the general formula (1) has a structure represented by the general formula (2) from the viewpoint of manifesting the effects of the present invention. Is preferable in terms of improving the stability of the compound.
  • the ⁇ -conjugated compound having the structure represented by the general formula (1) has a structure represented by the general formula (3) from the viewpoint of improving the stability of the compound.
  • the general formula (1) in at least one of R 5 and R 6 described, it represents an electron donating substituent also has R 5 and R 6 according to the general formula (1), It is preferable to represent an electron-donating substituent from the viewpoint of reducing ⁇ Est.
  • the ⁇ -conjugated compound having a structure represented by the general formula (1) preferably has a structure represented by the general formula (4) from the viewpoint of improving the stability of the compound.
  • R 5 and R 6 described in the general formula (1) are substituted or unsubstituted 9,9-dimethylacridinyl group, phenoxazinyl group, carbazolyl group, 5-phenylindoloindolyl group, or 5- It is preferable to represent a phenylphenazinyl group from the viewpoint of reducing ⁇ Est.
  • the ⁇ -conjugated compounds having the structure represented by the general formula (1) are A-1 to A-4, B-1 to B-5, C-1 to C-5, and C18 to C—. 21, having the structure represented by D-1 to D-5, E-1 to E-5 or F-1 to F-5 improves the stability of the compound and reduces ⁇ Est Is preferable.
  • the light emitting layer contains the ⁇ -conjugated compound and at least one of a fluorescent compound and a phosphorescent compound, so that the ⁇ -conjugated compound acts as a host compound and exhibits high luminous efficiency. This is preferable.
  • the light-emitting layer contains the ⁇ -conjugated compound, at least one of a fluorescent compound and a phosphorescent compound, and a host compound, so that the ⁇ -conjugated compound acts as an assist dopant. From the viewpoint of high luminous efficiency.
  • the organic electroluminescent element of this invention is used suitably for a display apparatus and an illuminating device.
  • the illumination device of the present invention is suitably used for a display device provided with a liquid crystal element as a display means.
  • the fluorescent compound according to the present invention has a structure represented by the general formula (1), and the absolute value ( ⁇ Est) of the energy difference between the lowest excited singlet level and the lowest triplet excited level is It is 0.5 eV or less.
  • the fluorescent compound according to the present invention is suitably used for a light-emitting thin film.
  • Organic EL emission methods There are two types of organic EL emission methods: “phosphorescence emission” that emits light when returning from the triplet excited state to the ground state, and “fluorescence emission” that emits light when returning from the singlet excited state to the ground state. is there.
  • phosphorescence emission that emits light when returning from the triplet excited state to the ground state
  • fluorescence emission that emits light when returning from the singlet excited state to the ground state.
  • TTA triplet-triplet annealing
  • the rate constant is usually small. That is, since the transition is difficult to occur, the exciton lifetime is increased from millisecond to second order, and it is difficult to obtain desired light emission.
  • the rate constant of the forbidden transition increases by three orders of magnitude or more due to the heavy atom effect of the central metal. % Phosphorescence quantum yield can be obtained.
  • a rare metal called a white metal such as iridium, palladium, or platinum, which is a rare metal. The price of the metal itself is a major industrial issue.
  • a general fluorescent compound is not necessarily a heavy metal complex like a phosphorescent compound, and is a so-called organic compound composed of a combination of general elements such as carbon, oxygen, nitrogen and hydrogen.
  • other non-metallic elements such as phosphorus, sulfur, and silicon can be used, and complexes of typical metals such as aluminum and zinc can be used.
  • high efficiency light emission such as phosphorescence emission cannot be expected.
  • TTA triplet-triplet annihilation
  • Thermal activated delayed fluorescence (TADF) compound which is another highly efficient fluorescent emission, is a method that can solve the problems of TTA.
  • the fluorescent compound has the advantage that the molecule can be designed infinitely. That is, among the molecularly designed compounds, there are compounds in which the absolute value of the energy level difference between the triplet excited state and the singlet excited state (hereinafter referred to as ⁇ Est) is extremely close (see FIG. 1). Although such a compound does not have a heavy atom in the molecule, a reverse intersystem crossing from a triplet excited state to a singlet excited state, which cannot normally occur due to a small ⁇ Est, occurs.
  • TADF can ideally emit 100% fluorescence.
  • Non-Patent Document 1 by introducing an electron-withdrawing skeleton such as a cyano group, a sulfonyl group, or triazine and an electron-donating skeleton such as a carbazole or diphenylamino group, LUMO and HOMO Are localized. It is also effective to reduce the change in molecular structure between the ground state and triplet excited state of the compound. As a method for reducing the structural change, for example, making the compound rigid is effective.
  • Rigidity described here means that there are few sites that can move freely in the molecule, for example, by suppressing free rotation in the bond between rings in the molecule or by introducing a condensed ring with a large ⁇ conjugate plane. means. In particular, it is possible to reduce the structural change in the excited state by making the portion involved in light emission rigid.
  • HOMO and LUMO are substantially separated in the molecule from the viewpoint of reducing ⁇ Est.
  • the distribution states of these HOMO and LUMO can be obtained from the electron density distribution when the structure is optimized obtained by semi-empirical molecular orbital calculation.
  • structure optimization and calculation of electron density distribution by semi-empirical molecular orbital calculation of a ⁇ -conjugated compound in the present invention are molecular orbital calculations using B3LYP as a functional and 6-31G (d) as a basis function. There is no particular limitation on the software, and any of them can be similarly calculated.
  • Gaussian 09 (Revision C.01, MJ Frisch, GW Trucks, H. B. Schlegel, GE Scuselia, M., manufactured by Gaussian, USA) is used.
  • HOMO and LUMO are substantially separated means that the HOMO orbital distribution calculated by the above molecular calculation and the central part of the LUMO orbital distribution are separated, more preferably the HOMO orbital distribution and the LUMO orbital. This means that the distributions of do not overlap.
  • the separation state of HOMO and LUMO from the above-mentioned structure optimization calculation using B3LYP as the functional and 6-31G (d) as the basis function, the time-dependent density functional method (Time-Dependent DFT) is used.
  • ⁇ Est is smaller, HOMO and LUMO are more separated.
  • ⁇ Est calculated using the same calculation method as described above is preferably 0.5 eV or less, more preferably 0.2 eV or less, and further preferably 0.1 eV or less.
  • ⁇ Est is 0.5 eV or less, the ⁇ -conjugated compound in the present invention exhibits thermally activated delayed fluorescence.
  • the fluorescence quantum yield is expressed as a ratio of the number of absorbed photons to the number of emitted photons. If all of the excited molecules return to the ground state by fluorescence, the fluorescence quantum yield becomes 1, but actually it does not become 1 by non-radiation deactivation. Non-radiation deactivation is a transition that returns to the ground state without emitting fluorescence. In addition to relaxation to the triplet state due to intersystem crossing, the energy of the electronic state is converted into vibrational energy and finally converted to thermal energy. Such as internal conversion and energy transfer to transfer energy to other molecules.
  • the present invention is characterized by a structure in which a biaryl structure is bridged with a heteroatom in order to suppress radiationless deactivation.
  • Preferred heteroatoms are those in which the electron orbital of the heteroatom interacts with the electron orbital of the biaryl structure.
  • Borol has an empty p-orbital of a boron atom interacting with a ⁇ * -orbital of a butadiene skeleton
  • Silole has a ⁇ * of two exocyclic substituents bonded to a silicon atom .
  • Molecular orbital calculation software reveals that the conjugated system is expanded by the interaction between the orbital and the ⁇ * orbital of the butadiene skeleton.
  • a conjugated system is expanded by using a hetero atom that interacts with an electron orbital of a biaryl structure in a bridging portion, and a skeleton having high planarity can be formed. Since non-radiation deactivation occurs when excitation energy changes to molecular structural change or vibrational energy, the present invention having a structure fixed to a plane can provide a ⁇ -conjugated compound with less non-radiation deactivation, Can provide a ⁇ -conjugated compound having a high fluorescence quantum yield.
  • a hole blocking layer also referred to as a hole blocking layer
  • an electron injection layer also referred to as a cathode buffer layer
  • An electron blocking layer also referred to as an electron barrier layer
  • a hole injection layer also referred to as an anode buffer layer
  • the electron transport layer used in the present invention is a layer 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. Moreover, you may be comprised by multiple layers.
  • the hole transport layer used in the present invention is a layer 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. Moreover, you may be comprised by multiple layers. In the above-described typical element configuration, the layer excluding the anode and the cathode is also referred to as “organic layer”.
  • the organic EL element of the present invention may be a so-called tandem element in which a plurality of light emitting units including at least one light emitting layer are stacked.
  • a tandem element in which a plurality of light emitting units including at least one light emitting layer are stacked.
  • the first light emitting unit, the second light emitting unit and the third light emitting unit are all the same, May be different.
  • Two light emitting units may be the same, and the remaining one may be different.
  • a plurality of light emitting units may be laminated directly or via an intermediate layer, and the intermediate layer is generally an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, an intermediate layer.
  • a known material structure can be used as long as it is also called an insulating layer and has a function of supplying electrons to the anode-side adjacent layer and holes to the cathode-side adjacent layer.
  • Examples of materials used for the intermediate layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO 2 , TiN, ZrN, HfN, TiO x , VO x , CuI, InN, GaN, Conductive inorganic compound layers such as CuAlO 2 , CuGaO 2 , SrCu 2 O 2 , LaB 6 , RuO 2 , Al, etc., two-layer films such as Au / Bi 2 O 3 , SnO 2 / Ag / SnO 2 , ZnO / Multi-layer film such as Ag / ZnO, Bi 2 O 3 / Au / Bi 2 O 3 , TiO 2 / TiN / TiO 2 , TiO 2 / ZrN / TiO 2 , fullerenes such as C 60 , conductivity such as oligothiophene Examples include organic material layers, conductive organic compound layers such as metal phthalocyanines, metal-free phthalocyanines
  • tandem organic EL element examples include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6,107,734, US Pat. No. 6,337,492, International JP 2005/009087, JP 2006-228712, JP 2006-24791, JP 2006-49393, JP 2006-49394, JP 2006-49396, JP 2011. No. -96679, JP 2005-340187, JP 47114424, JP 34966681, JP 3884564, JP 4213169, JP 2010-192719, JP 2009-076929.
  • the present invention is not limited to these.
  • the light-emitting layer used in the present invention is a layer that provides a field in which electrons and holes injected from an electrode or an adjacent layer are recombined to emit light via excitons, and the light-emitting portion is the light-emitting layer. Even in the layer, it may be the interface between the light emitting layer and the adjacent layer. If the light emitting layer used for this invention satisfy
  • the total thickness of the light emitting layer is not particularly limited, but it prevents the uniformity of the film to be formed, the application of unnecessary high voltage during light emission, and the improvement of the stability of the emission color against the drive current.
  • each light emitting layer used in the present invention is preferably adjusted within the range of 2 nm to 1 ⁇ m, more preferably adjusted within the range of 2 to 200 nm, and further preferably 3 to 150 nm. Adjusted within range.
  • the light-emitting layer used in the present invention contains a light-emitting dopant (a light-emitting compound, a light-emitting dopant compound, a dopant compound, or simply a dopant), and further a host compound (matrix material, light-emitting host compound, or simply a host). .) Is preferably contained.
  • Luminescent dopant As the luminescent dopant, a fluorescent luminescent dopant (also referred to as a fluorescent luminescent compound, a fluorescent dopant, or a fluorescent compound), a delayed fluorescent dopant, a phosphorescent dopant (phosphorescent compound, phosphorescence). (Also referred to as a dopant or a phosphorescent compound) is preferably used.
  • at least one light emitting layer has a structure represented by the above general formula (1) and contains a ⁇ -conjugated compound having ⁇ Est of 0.5 eV or less as a light emitting dopant or an assist dopant. It is characterized by that.
  • the light emitting layer contains the ⁇ -conjugated compound in a range of 5 to 40% by mass, and particularly preferably in a range of 10 to 30% by mass.
  • concentration of the ⁇ -conjugated compound in the light-emitting layer can be arbitrarily determined based on the specific ⁇ -conjugated compound used and the device requirements, and is uniform with respect to the thickness direction of the light-emitting layer. It may be contained in various concentrations, and may have any concentration distribution.
  • the ⁇ -conjugated compound according to the present invention may be used in combination of two or more types, a combination of ⁇ -conjugated compounds having different structures, or a combination of a ⁇ -conjugated compound and a phosphorescent compound. It may be used. Thereby, arbitrary luminescent colors can be obtained.
  • the light emission color of the organic EL device of the present invention and the compound used in the present invention is shown in FIG. 3.16 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 luminance meter CS-1000 (manufactured by Konica Minolta Co., Ltd.) is applied to the CIE chromaticity coordinates.
  • the light emitting layer of one layer or a plurality of layers contains a plurality of light emitting dopants having different emission colors and emits white light.
  • the ⁇ -conjugated compound according to the present invention has a structure represented by the following general formula (1), and has a ⁇ Est of 0.5 eV or less.
  • X 1 represents Si—R 1 (R 2 ), B—R 3 , O, P— (R 4 ) O, SO, or SO 2 .
  • R 1 to R 4 each independently represents a substituent.
  • C 1 to C 4 each represent a carbon atom.
  • Z1 represents together with C 1 and C 2 and Z2 together with C 3 and C 4 each represents an atomic group necessary for forming an aromatic hydrocarbon ring.
  • R 5 and R 6 each independently represents a substituent.
  • n1 and n2 each independently represents an integer of 1 to 4.
  • Each substituent may be the same or different, and each substituent may be bonded to form a ring.
  • At least one of R 5 and R 6 represents an electron donating group or a group substituted with an electron donating group.
  • Examples of the substituent for R 1 to R 4 in the general formula (1) 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).
  • Aromatic hydrocarbon groups also called aromatic hydrocarbon ring groups, aromatic carbocyclic groups, aryl groups, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group
  • Aromatic hydrocarbon groups also called aromatic hydrocarbon ring groups, aromatic carbocyclic groups, aryl groups, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group
  • azulenyl group acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl , Biphenylyl group, etc.
  • aromatic heterocyclic group eg, pyr
  • substituents may be further substituted with the above substituents. Further, these substituents may be bonded together to form a ring.
  • Examples of the aromatic hydrocarbon ring formed together with C 1 , C 2 and Z 1 in the general formula (1) and the aromatic hydrocarbon ring formed together with C 3 , C 4 and Z 2 include a benzene ring, a biphenyl ring, and naphthalene.
  • Ring azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, Examples include a fluoranthrene ring, a naphthacene ring, a pentacene ring, a perylene ring, a pentaphen ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthrathrene ring. Of these, a benzene ring is preferably used.
  • n1 and n2 each independently represents an integer of 1 to 4.
  • n1 and n2 may be the same or different, but are preferably the same.
  • the plurality of R 5 present in the molecule may be the same as or different from each other. The same applies to n2.
  • R 5 and R 6 is preferably an electron donating substituent, more preferably R 5 and R 6 is represented by an electron donating substituent It is.
  • the electron-donating substituent used here means that the LUMO level of the structure other than R 5 and R 6 is LUMO1, and the LUMO level of the electron-donating substituent represented by R 5 or R 6 is LUMO2. When expressed, it means a structure having a relationship of LUMO1> LUMO2.
  • R 5 and R 6 described in the general formula (1) are substituted or unsubstituted 9,9-dimethylacridinyl group, phenoxazinyl group, carbazolyl group, 5-phenylindoloindolyl group, or 5-phenyl It preferably represents a phenazinyl group.
  • the ⁇ -conjugated compound having the structure represented by the general formula (1) has a structure represented by the following general formula (2).
  • X 1 similarly to the X 1 in the general formula (1), Si-R 1 (R 2), B-R 3, O, P- (R 4) O, SO, or representing the SO 2.
  • R 1 ⁇ R 4 similar to R 1 ⁇ R 4 in the general formula (1), each independently represent a substituent.
  • C 3 and C 4 like the C 3 and C 4 in the general formula (1), each represent a carbon atom.
  • n1 and n2 each independently represents an integer of 1 to 4 as in the case of n1 and n2 in the general formula (1).
  • the ⁇ -conjugated compound having the structure represented by the general formula (1) has a structure represented by the following general formula (3).
  • X 1 similarly to the X 1 in the general formula (1), Si-R 1 (R 2), B-R 3, O, P- (R 4) O, SO, or representing the SO 2.
  • R 1 ⁇ R 4 similar to R 1 ⁇ R 4 in the general formula (1), each independently represent a substituent.
  • n1 and n2 each independently represents an integer of 1 to 4 as in the case of n1 and n2 in the general formula (1).
  • the ⁇ -conjugated compound having the structure represented by the general formula (1) has a structure represented by the following general formula (4).
  • X 1 similarly to the X 1 in the general formula (1), Si-R 1 (R 2), B-R 3, O, P- (R 4) O, SO, or representing the SO 2.
  • R 1 ⁇ R 4 similar to R 1 ⁇ R 4 in the general formula (1), each independently represent a substituent.
  • R 5 and R 6 each independently represents a substituent.
  • the phosphorescent dopant used in 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.), and a phosphorescence quantum yield. Is defined as a compound of 0.01 or more at 25 ° C., but a preferable phosphorescence quantum yield is 0.1 or more.
  • the phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant used in the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. Just do it.
  • the phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL device.
  • Specific examples of known phosphorescent dopants that can be used in the present invention include compounds described in the following documents. Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006 /. No. 0202194, U.S. Patent Application Publication No.
  • a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, and metal-sulfur bond is preferable.
  • Fluorescent compound capable of being used in combination with ⁇ -conjugated compound A fluorescent compound (also referred to as a fluorescent dopant) that can be used in combination with the ⁇ -conjugated compound according to the present invention will be described.
  • the fluorescent compound that can be used in combination with the ⁇ -conjugated compound according to the present invention is not particularly limited, and for example, a fluorescent compound having a ⁇ Est of greater than 0.5 eV can be suitably used.
  • the host compound used in the present invention is a compound mainly responsible for charge injection and transport in the light emitting layer, and its own light emission is not substantially observed in the organic EL device.
  • the host compound preferably has a mass ratio in the layer of 20% or more among the compounds contained in the light emitting layer.
  • a host compound may be used independently or may be used in combination of multiple types. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient.
  • the host compound that is preferably used in the present invention will be described below.
  • the host compound used together with the ⁇ -conjugated compound in the present invention is not particularly limited, but those having an excitation energy larger than the excitation singlet energy of the ⁇ -conjugated compound according to the present invention are preferable from the viewpoint of reverse energy transfer. Furthermore, those having an excitation triplet energy larger than the excitation triplet energy of the ⁇ -conjugated compound according to the present invention are more preferable.
  • the host compound is responsible for carrier transport and exciton generation in the light emitting layer. Therefore, it can exist stably in all active species states such as cation radical state, anion radical state, and excited state, and does not cause chemical changes such as decomposition and addition reaction. It is preferable not to move at the angstrom level.
  • the light-emitting dopant used in combination exhibits TADF light emission
  • the T 1 energy of the host compound itself is high, and the host compounds are associated with each other.
  • the host compound does not decrease in T 1 , such as not creating a low T 1 state
  • TADF compound and the host compound do not form an exciplex, or the host compound does not form an electromer due to an electric field.
  • Appropriate design is required.
  • the host compound itself must have high electron hopping mobility, high hole hopping movement, and small structural change when it is in a triplet excited state. It is.
  • host compounds that satisfy such requirements include an extended ⁇ -conjugated skeleton having a high T 1 energy and a 14 ⁇ electron system, such as a carbazole skeleton, an azacarbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, or an azadibenzofuran skeleton.
  • a carbazole skeleton such as a carbazole skeleton, an azacarbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, or an azadibenzofuran skeleton.
  • What has as a partial structure is mentioned preferably.
  • the light-emitting layer contains a carbazole derivative, it is possible to promote appropriate carrier hopping and dispersion of the light-emitting material in the light-emitting layer, and the effect of improving the light-emitting performance of the device and the stability of the thin film can be obtained. Therefore, it
  • aryl includes not only an aromatic hydrocarbon ring but also an aromatic heterocyclic ring. More preferably, it is a compound in which a carbazole skeleton and a 14 ⁇ -electron aromatic heterocyclic compound having a molecular structure different from that of the carbazole skeleton are directly bonded, and further a 14 ⁇ -electron aromatic heterocyclic compound is incorporated in the molecule.
  • a carbazole derivative having at least one is preferred.
  • the carbazole derivative is preferably a compound having two or more conjugated structures having 14 ⁇ electrons or more in order to further enhance the effects of the present invention.
  • the preferred host compound used in the present invention may be a low molecular compound having a molecular weight that can be purified by sublimation or a polymer having a repeating unit.
  • a low molecular weight compound sublimation purification is possible, so that there is an advantage that purification is easy and a high-purity material is easily obtained.
  • the molecular weight is not particularly limited as long as sublimation purification is possible, but the preferred molecular weight is 3000 or less, more preferably 2000 or less.
  • the host compound has a hole transporting ability or an electron transporting ability, prevents the emission of light from being long-wavelength, and is stable with respect to heat generated when the organic EL element is driven at a high temperature or during the driving of the element.
  • Tg glass transition temperature
  • Tg is preferably 90 ° C. or higher, more preferably 120 ° C. or higher.
  • the glass transition point (Tg) is a value determined by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).
  • host compound used in the present invention examples include compounds represented by H-1 to H231 described in paragraphs [0255] to [0293] of JP-A-2015-38941, and the following H- Although compounds represented by 232 to H-236 are exemplified, host compounds usable in the present invention are not limited thereto.
  • the ⁇ -conjugated compound according to the present invention has a structure represented by the general formula (1) and ⁇ Est is 0.5 eV or less, It is preferable to contain a fluorescent and / or phosphorescent compound from the viewpoint of high luminous efficiency.
  • the light emitting layer may or may not contain a host compound, but is preferably contained.
  • the ⁇ -conjugated compound, the luminescent compound, and the host compound according to the present invention are not limited in the number of components in the light-emitting layer, but the ⁇ -conjugated compound and the luminescent compound are each contained one by one, and the host None or one compound is preferably contained, and it is more preferred that one ⁇ -conjugated compound, one light-emitting compound, and one host compound are contained.
  • the ⁇ -conjugated compound according to the present invention acts as an assist dopant.
  • the ⁇ -conjugated compound according to the present invention acts as a host compound.
  • the mechanism for producing the effect is the same in any case, and the triplet exciton generated on the ⁇ -conjugated compound according to the present invention is converted into a singlet exciton by reverse intersystem crossing (RISC). It is in. Thereby, all the exciton energies generated theoretically on the ⁇ -conjugated compound according to the present invention can be transferred to the luminescent compound, and high luminous efficiency can be realized.
  • RISC reverse intersystem crossing
  • FIG. 3A and FIG. 3B show schematic diagrams when the ⁇ -conjugated compound according to the present invention acts as an assist dopant and a host compound, respectively.
  • the generation process of triplet excitons generated on the ⁇ -conjugated compound according to the present invention is not limited to electric field excitation, and includes energy transfer and electron transfer from the light emitting layer or from the peripheral layer interface.
  • a fluorescent material is used as a light emitting material.
  • the present invention is not limited to this, and a phosphorescent compound may be used, or a fluorescent compound and phosphorescent light emission. Both of the functional compounds may be used.
  • a host compound having a mass ratio of 100% or more with respect to the ⁇ -conjugated compound is present, and fluorescence and / or phosphorescence emission
  • the light emitting layer is preferably contained in the active compound in a mass ratio of 0.1% to 50% with respect to the ⁇ -conjugated compound.
  • Energy levels of S 1 and T 1 of the ⁇ -conjugated compounds according to the present invention is lower than the energy level of the S 1 and T 1 of the host material, from the energy level of the S 1 and T 1 of the light-emitting compound Higher is preferable.
  • the fluorescent and / or phosphorescent compound is in a mass ratio of 0.1% to 50 with respect to the ⁇ -conjugated compound.
  • a light emitting layer containing at most% is preferred.
  • the energy levels of S 1 and T 1 of the ⁇ -conjugated compound according to the present invention are preferably higher than the energy levels of S 1 and T 1 of the luminescent compound.
  • a ⁇ -conjugated compound having ⁇ Est of 0.5 eV or less according to the present invention is used as an assist dopant or host compound, it is preferable that the emission spectrum of the ⁇ -conjugated compound and the absorption spectrum of the luminescent compound overlap.
  • the electron transport layer is made of a material having a function of transporting electrons, and may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • the total thickness of the electron transport layer according to the present invention is not particularly limited, but is usually in the range of 2 nm to 5 ⁇ m, more preferably 2 to 500 nm, and further preferably 5 to 200 nm.
  • the organic EL element when the light generated in the light emitting layer is extracted from the electrode, the light extracted directly from the light emitting layer interferes with the light extracted after being reflected by the electrode from which the light is extracted and the electrode located at the counter electrode. It is known to wake up.
  • the electron mobility of the electron transport layer is preferably 10 ⁇ 5 cm 2 / Vs or more.
  • the material used for the electron transport layer may be any of electron injecting or transporting properties and hole blocking properties, and can be selected from conventionally known compounds. Can be selected and used.
  • nitrogen-containing aromatic heterocyclic derivatives (carbazole derivatives, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring are substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, Triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, azatriphenylene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzthiazole derivatives, etc.), dibenzofuran derivatives, Dibenzothiophene derivatives, silole derivatives, aromatic hydrocarbon ring derivatives (naphthalene derivatives, anthracene derivatives, triphenylene derivatives, etc.) It is.
  • a metal complex having a quinolinol skeleton or a dibenzoquinolinol skeleton as a ligand such as tris (8-quinolinol) aluminum (Alq), 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), etc.
  • a metal complex in which the central metal is replaced with In, Mg, 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 transport 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.
  • 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.
  • the electron transport layer may be doped with a doping material as a guest material to form an electron transport layer having a high n property (electron rich).
  • the doping material include n-type dopants such as metal complexes and metal compounds such as metal halides.
  • Specific examples of the electron transport layer having such a structure include, for example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. , 95, 5773 (2004) and the like.
  • More preferable electron transport materials in the present invention include aromatic heterocyclic compounds containing at least one nitrogen atom.
  • aromatic heterocyclic compounds containing at least one nitrogen atom For example, pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, azadibenzofuran derivatives. , Azadibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, benzimidazole derivatives, and the like.
  • the electron transport material may be used alone or in combination of two or more.
  • the hole blocking layer is a layer having a function of an electron transport layer in a broad sense, and is preferably made of a material having a function of transporting electrons while having a small ability to transport holes, and transporting electrons while transporting holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the electron carrying layer mentioned above can be used as a hole-blocking layer concerning this invention as needed.
  • the hole blocking layer provided in the organic EL device of the present invention is preferably provided adjacent to the cathode side of the light emitting layer.
  • the layer thickness of the hole blocking layer according to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • the material used for the hole blocking layer the material used for the above-described electron transport layer is preferably used, and the material used as the above-described host compound is also preferably used for the hole blocking layer.
  • the electron injection layer (also referred to as “cathode buffer layer”) according to the present invention is a layer provided between the cathode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. It is described in detail in Chapter 2 “Electrode Materials” (pages 123 to 166) of the second edition of “The Forefront of Industrialization (issued by NTT Corporation on November 30, 1998)”.
  • the electron injection layer may be provided as necessary, and may be present between the cathode and the light emitting layer or between the cathode and the electron transport layer as described above.
  • the electron injection layer is preferably a very thin film, and the layer thickness is preferably in the range of 0.1 to 5 nm depending on the material. Moreover, the nonuniform layer (film
  • JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like Specific examples of materials preferably used for the electron injection layer are as follows. , Metals typified by strontium and aluminum, alkali metal compounds typified by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkaline earth metal compounds typified by magnesium fluoride, calcium fluoride, etc., oxidation Examples thereof include metal oxides typified by aluminum, metal complexes typified by 8-hydroxyquinolinate lithium (Liq), and the like. Further, the above-described electron transport material can also be used. Moreover, the material used for said electron injection layer may be used independently, and may be used in combination of multiple types.
  • the hole transport layer is made of a material having a function of transporting holes and may have a function of transmitting holes injected from the anode to the light emitting layer.
  • the total thickness of the hole transport layer according to the present invention is not particularly limited, but is usually in the range of 0.5 nm to 5 ⁇ m, more preferably 2 to 500 nm, and further preferably 5 to 200 nm.
  • a material used for the hole transport layer hereinafter referred to as a hole transport material
  • any material that has either a hole injection property or a transport property or an electron barrier property may be used. Any one can be selected and used.
  • porphyrin derivatives for example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives , Indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, and polyvinyl carbazole, polymer materials or oligomers with aromatic amines introduced into the main chain or side chain, polysilane, conductive And polymer (for example, PEDOT / PSS, aniline copolymer, polyaniline, polythiophene, etc.).
  • PEDOT / PSS aniline copolymer, poly
  • triarylamine derivatives examples include benzidine type typified by ⁇ -NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), starburst type typified by MTDATA, Examples include compounds having fluorene or anthracene in the triarylamine-linked core.
  • hexaazatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as hole transport materials.
  • a hole transport layer having a high p property doped with impurities can also be used. 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.
  • JP-A-11-251067, J. Org. Huang et. al. It is also possible to use so-called p-type hole transport materials and inorganic compounds such as p-type-Si and p-type-SiC, as described in the literature (Applied Physics Letters 80 (2002), p. 139). Further, ortho-metalated organometallic complexes having Ir or Pt as the central metal as typified by Ir (ppy) 3 are also preferably used.
  • the above-mentioned materials can be used as the hole transport material, a triarylamine derivative, a carbazole derivative, an indolocarbazole derivative, an azatriphenylene derivative, an organometallic complex, or an aromatic amine is introduced into the main chain or side chain.
  • the polymer materials or oligomers used are preferably used.
  • the hole transport material may be used alone or in combination of two or more.
  • the electron blocking layer is a layer having a function of a hole transport layer in a broad sense, and is preferably made of a material having a function of transporting holes and a small ability to transport electrons, while transporting holes. By blocking electrons, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned above can be used as an electron blocking layer according to the present invention, if necessary.
  • the electron blocking layer provided in the organic EL device of the present invention is preferably provided adjacent to the anode side of the light emitting layer.
  • the layer thickness of the electron blocking layer according to the present invention is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.
  • the material used for the electron blocking layer the material used for the above-described hole transport layer is preferably used, and the above-mentioned host compound is also preferably used for the electron blocking layer.
  • the hole injection layer (also referred to as “anode buffer layer”) according to the present invention is a layer provided between the anode and the light emitting layer for the purpose of lowering the driving voltage and improving the light emission luminance. It is described in detail in Volume 2, Chapter 2, “Electrode Materials” (pages 123 to 166) of “The Forefront of Industrialization (issued by NTT Corporation on November 30, 1998)”.
  • the hole injection layer may be provided as necessary, and may be present between the anode and the light emitting layer or between the anode and the hole transport layer as described above.
  • the details of the hole injection layer are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc.
  • materials used for the hole injection layer include: Examples thereof include materials used for the above-described hole transport layer. Among them, phthalocyanine derivatives typified by copper phthalocyanine, hexaazatriphenylene derivatives, metal oxides typified by vanadium oxide, amorphous carbon as described in JP-T-2003-519432 and JP-A-2006-135145, etc.
  • the materials used for the hole injection layer described above may be used alone or in combination of two or more.
  • the organic layer in the present invention described above may further contain other additives.
  • the additive include halogen elements such as bromine, iodine and chlorine, halogenated compounds, alkali metals such as Pd, Ca and Na, alkaline earth metals, transition metal compounds, complexes, and salts.
  • the content of the additive can be arbitrarily determined, but is preferably 1000 ppm or less, more preferably 500 ppm or less, and further preferably 50 ppm or less with respect to the total mass% of the contained layer. . However, it is not within this range depending on the purpose of improving the transportability of electrons and holes or the purpose of favoring the exciton energy transfer.
  • a method for forming an organic layer (hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) according to the present invention will be described.
  • the method for forming the organic layer according to the present invention is not particularly limited, and a conventionally known method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used.
  • the wet method include spin coating method, casting method, ink jet method, printing method, die coating method, blade coating method, roll coating method, spray coating method, curtain coating method, and LB method (Langmuir-Blodgett method). From the viewpoint of obtaining a homogeneous thin film easily and high productivity, a method with high roll-to-roll method suitability such as a die coating method, a roll coating method, an ink jet method and a spray coating method is preferable.
  • liquid medium for dissolving or dispersing the organic EL material used in 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, Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
  • ketones such as methyl ethyl ketone and cyclohexanone
  • fatty acid esters such as ethyl acetate
  • halogenated hydrocarbons such as dichlorobenzene, toluene, xylene
  • Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene
  • a dispersion method it can disperse
  • different film formation methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁇ 6 to 10 ⁇ 2 Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within the range of 50 nm / second, substrate temperature ⁇ 50 to 300 ° C., layer (film) thickness 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the organic layer according to the present invention is preferably formed from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film formation methods. In that case, it is preferable to perform the work in a dry inert gas atmosphere.
  • anode As the anode in the organic EL element, a material having a work function (4 eV or more, preferably 4.5 eV or more) of a metal, an alloy, an electrically conductive compound, or a mixture thereof is preferably used.
  • electrode substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • 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) that can form a transparent conductive film may be used.
  • a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not 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%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the anode depends on the material, it is usually selected within the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
  • cathode As the cathode, a material having a 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. Specific examples of such 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, aluminum, 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
  • a magnesium / aluminum mixture a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like.
  • 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 film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or translucent cathode can be produced by producing a conductive transparent material mentioned in the description of the anode on the cathode after producing the above metal with a thickness of 1 to 20 nm.
  • the 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 is not particularly limited in the type of glass, plastic, etc., and is transparent. Or 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 (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, 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 or polyarylates, Arton (trade name, manufactured by JSR) or Appel (
  • a material other than the transparent resin can be selected.
  • a metal such as copper, copper alloy, aluminum, aluminum alloy, gold, nickel, titanium, stainless steel, and tin. Is mentioned. One of these may be used alone, or two or more of these may be mixed or multilayered.
  • the thickness of the element substrate is not particularly limited, but is preferably 50 ⁇ m to 500 ⁇ m in view of molding processability, handling property, and the like.
  • the thickness of the element substrate can be measured using a micrometer.
  • 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 the oxygen permeability measured by a method according to JIS K 7126-1987.
  • it is preferably a high-barrier film having 1 ⁇ 10 ⁇ 3 mol / m 2 ⁇ s ⁇ Pa or less and a water vapor permeability of 1 ⁇ 10 ⁇ 5 g / m 2 ⁇ 24 h or less.
  • any material may be used as long as it 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 can be used.
  • stacking order of an inorganic layer and an organic layer It is preferable to laminate
  • the method for forming the barrier film is not particularly limited.
  • vacuum deposition sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization
  • a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or 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, and ceramic substrates.
  • the external extraction quantum efficiency at room temperature (25 ° C.) of light emission of the organic EL device of the present invention is preferably 1% or more, and more preferably 5% or more.
  • external extraction quantum efficiency (%) number of photons emitted to the outside of the organic EL element / number of electrons flowed 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.
  • sealing means used for sealing the organic EL element of the present invention include a method of bonding a sealing member, an electrode, and a support substrate with an adhesive.
  • a sealing member it should just be arrange
  • transparency and electrical insulation are not particularly limited. Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • polymer plate examples include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • metal plate examples 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 organic EL 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 mol / m 2 ⁇ s ⁇ Pa or less, and is measured by a method according to JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity 90 ⁇ 2%) is preferably 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ 24 h or less.
  • 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 adhesive-hardened from room temperature to 80 degreeC is preferable.
  • a desiccant may be dispersed in the adhesive.
  • coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print 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, ion plating, plasma polymerization, atmospheric pressure plasma
  • a combination 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.
  • a vacuum can also be used.
  • a hygroscopic compound can also be enclosed inside. Examples of the hygroscopic compound 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 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 outside the sealing film or the sealing film on the side facing the support substrate with the organic layer interposed therebetween.
  • 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, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
  • An organic EL element emits light inside a layer having a refractive index higher than that of air (within a refractive index of about 1.6 to 2.1), and is about 15% to 20% of light generated in the light emitting layer. It is generally said that it can only be taken out. 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 light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the side surface of the device.
  • a technique 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 transparent substrate and the air interface (for example, US Pat. No. 4,774,435), A method for improving efficiency by providing light condensing property (for example, Japanese Patent Laid-Open No. 63-134795), a method for forming a reflective surface on the side surface of an element (for example, Japanese Patent Laid-Open No. 1-220394), a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the substrate and the light emitter (for example, 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.
  • an element excellent in high luminance or durability can be obtained by combining these means.
  • the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally in the range of about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Furthermore, it is preferable that it is 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 diminished 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 has a feature that the effect of improving the light extraction efficiency is high.
  • 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 or second-order diffraction.
  • the light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating into any layer or medium (in the transparent substrate or transparent electrode). , Trying to extract light out.
  • the introduced diffraction grating desirably 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. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any 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 in the range of about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL element of the present invention can be processed to provide a structure on a microlens array, for example, on the light extraction side of a support substrate (substrate), or combined with a so-called condensing sheet, for example, in a specific direction, for example, the element Condensing light in the front direction with respect to the light emitting surface can increase the luminance in a specific direction.
  • a microlens array 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 within a range of 10 to 100 ⁇ m.
  • the condensing sheet for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • 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 and a film together with a condensing sheet For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • the organic EL element of the present invention can be used as an electronic device such as a display device, a display, and various light emitting devices.
  • light emitting devices include lighting devices (home lighting, interior lighting), clocks and backlights for liquid crystals, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of 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. In the fabrication of the element, a conventionally known method is used. Can do.
  • the display device including the organic EL element 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 vapor deposition, casting, spin coating, ink jet, printing, or the like.
  • vapor deposition there is no limitation on the method, but a vapor deposition method, an inkjet method, a spin coating method, and a printing method are preferable.
  • the configuration of the organic EL element included in the display device is selected from the above-described configuration examples of the organic EL element as necessary.
  • the manufacturing method of an organic EL element is as having shown in the one aspect
  • 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, or various light emission 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.
  • Examples of the display device or display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile.
  • it may be used as a display device for reproducing still images and moving images
  • 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 devices include household lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, optical storage media light sources, electrophotographic copying machine light sources, optical communication processor light sources, optical sensor light sources, etc.
  • the present invention is not limited to these.
  • FIG. 4 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, a wiring unit C that electrically connects the display unit A and the control unit B, and the like.
  • the control unit B is electrically connected to the display unit A via the wiring unit C, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside. Sequentially emit light according to the image data signal, scan the image, and display the image information on the display unit A.
  • FIG. 5 is a schematic diagram of a display device using an active matrix method.
  • the display unit A includes a wiring unit C including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate.
  • the main members of the display unit A will be described below.
  • FIG. 5 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 receives an image data signal from the data line 6 and emits light according to the received image data.
  • Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 6 is a schematic diagram showing a pixel circuit.
  • 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, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.
  • 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 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 element 10 of each of the plurality of pixels, and the light emission of the organic EL element 10 of each of the plurality of pixels 3. 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.
  • a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.
  • FIG. 7 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 scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal.
  • the pixel 3 has no active element, and the manufacturing cost can be reduced.
  • the organic EL element of the present invention By using the organic EL element of the present invention, a display device with improved luminous efficiency was obtained.
  • the organic EL element of the present invention can also be used for a lighting device.
  • the organic EL element of the present invention may be used as an organic EL element having a resonator structure.
  • Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.
  • the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection apparatus for projecting an image, or a type for directly viewing a still image or a moving image. It may be used as a display device (display).
  • the driving method when used as a display device for reproducing a moving image may be either a passive matrix method or an active matrix method. Alternatively, it is possible to produce a full-color display device by using two or more organic EL elements of the present invention having different emission colors.
  • the fluorescent compound used in the present invention can be applied to an organic EL element that emits substantially white light as a lighting device.
  • white light emission can be obtained by simultaneously emitting a plurality of light emission colors and mixing the colors.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of three primary colors of red, green, and blue, or two of the complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.
  • the method for forming the organic EL device of the present invention may be simply arranged by providing a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, or the like, and separately coating with the mask. Since the other layers are common, patterning of a mask or the like is unnecessary, and for example, an electrode film can be formed on one surface 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 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 emit white light.
  • FIG. 1 One Embodiment of Lighting Device of the Present Invention.
  • 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. 1 An epoxy photocurable adhesive
  • FIG. 8 shows a schematic diagram of a lighting device, and the organic EL element (organic EL element 101 in the lighting device) of the present invention is covered with a glass cover 102 (note that the sealing operation with the glass cover is performed by lighting. This was 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 in the apparatus into contact with the air.
  • FIG. 9 is a cross-sectional view of the lighting device, 105 is a cathode, 106 is an organic layer, and 107 is a glass substrate with a transparent electrode.
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • the ⁇ -conjugated compound according to the present invention can also be used for a light-emitting thin film, a display device, and a lighting device.
  • the luminescent thin film of the present invention will be described.
  • the light-emitting thin film of the present invention can be produced in the same manner as the organic layer forming method.
  • the method for forming the light-emitting thin film of the present invention is not particularly limited, and a conventionally known method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used.
  • the wet method include spin coating method, casting method, ink jet method, printing method, die coating method, blade coating method, roll coating method, spray coating method, curtain coating method, and LB method (Langmuir-Blodgett method). From the viewpoint of obtaining a homogeneous thin film easily and high productivity, a method with high roll-to-roll method suitability such as a die coating method, a roll coating method, an ink jet method and a spray coating method is preferable.
  • liquid medium for dissolving or dispersing the ⁇ -conjugated compound used in 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 and xylene.
  • Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, and organic solvents such as DMF and DMSO can be used.
  • dispersion method it can disperse
  • different film formation methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is in the range of 50 to 450 ° C., and the degree of vacuum is in the range of 10 ⁇ 6 to 10 ⁇ 2 Pa.
  • the deposition rate is within the range of 0.01 to 50 nm / second
  • the substrate temperature is within the range of ⁇ 50 to 300 ° C.
  • the layer thickness is within the range of 0.1 to 5 ⁇ m, and preferably within the range of 5 to 200 nm. desirable.
  • the luminescent thin film of this invention can also be used for a display apparatus and an illuminating device. As a result, a display device and a lighting device with improved luminous efficiency can be obtained.
  • Example 2 (Preparation of organic EL element 2-1) An ITO (indium tin oxide) film having a thickness of 150 nm was formed on a 50 mm ⁇ 50 mm ⁇ 0.7 mm thick glass substrate, followed by patterning to form an ITO transparent electrode as an anode.
  • the transparent substrate provided with the ITO transparent electrode was subjected to ultrasonic cleaning with isopropyl alcohol and dried with dry nitrogen gas, followed by UV ozone cleaning for 5 minutes.
  • the obtained transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus.
  • Each of the resistance heating boats for vapor deposition in the vacuum vapor deposition apparatus was filled with an optimum amount for each element of the constituent material of each layer.
  • the resistance heating boat was made of molybdenum or tungsten.
  • the vacuum deposition apparatus After depressurizing the inside of the vacuum deposition apparatus to a vacuum degree of 1 ⁇ 10 ⁇ 4 Pa, it was heated by energizing a resistance heating boat containing HI-1, and deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second, A hole injection layer having a thickness of 15 nm was formed.
  • ⁇ -NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • a resistance heating boat containing comparative compound 1 as a host material and GD-1 as a luminescent compound was energized and heated, and the hole transport layer was deposited at a deposition rate of 0.1 nm / second and 0.010 nm / second, respectively. Co-evaporated on top to form a 40 nm thick light emitting layer.
  • HB-1 was deposited at a deposition rate of 0.1 nm / second to form a first electron transport layer having a thickness of 5 nm.
  • ET-1 was deposited thereon at a deposition rate of 0.1 nm / second to form a second electron transport layer having a thickness of 45 nm.
  • lithium fluoride was vapor-deposited so as to have a thickness of 0.5 nm, and then 100 nm of aluminum was vapor-deposited to form a cathode, thereby producing an organic EL element 2-1.
  • the obtained organic EL device was allowed to emit light at room temperature (about 25 ° C.) and a constant current of 2.5 mA / cm 2 . Then, the light emission luminance of the organic EL element immediately after the start of light emission was measured using a spectral radiance meter CS-2000 (manufactured by Konica Minolta). The obtained light emission luminance was applied to the following equation, and the relative light emission luminance with respect to the light emission luminance of the organic EL element 1-1 was determined.
  • Relative light emission luminance (light emission luminance of each organic EL element / light emission luminance of organic EL element 1-1) ⁇ 100
  • Example 3 (Preparation of organic EL element 3-1) An ITO (indium tin oxide) film having a thickness of 150 nm was formed as an anode on a glass substrate having a size of 50 mm ⁇ 50 mm and a thickness of 0.7 mm, followed by patterning. Thereafter, the transparent substrate with the ITO transparent electrode is ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. Then, the transparent substrate is placed on a substrate holder of a commercially available vacuum deposition apparatus. Fixed. Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication. As the evaporation crucible, a crucible made of a resistance heating material made of molybdenum or tungsten was used.
  • the deposition crucible containing ⁇ -NPD was energized and heated, and deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second. A hole injection transport layer was formed.
  • mCP as a host compound and Comparative Compound 1 as a dopant were co-deposited at a deposition rate of 0.1 nm / second so as to be 90% and 10% by volume, respectively, to form a light emitting layer having a layer thickness of 35 nm.
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • Organic EL elements 3-2 to 3-31 were produced in the same manner as the organic EL element 3-1, except that the dopant was changed as shown in Table 3.
  • Example 4 (Preparation of organic EL element 4-1) Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • a substrate NH45 manufactured by NH Techno Glass Co., Ltd.
  • ITO indium tin oxide
  • This transparent support substrate using a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water, 3000 rpm, A thin film was formed by spin coating under conditions of 30 seconds, and then dried at 200 ° C. for 1 hour to provide a hole injection layer having a layer thickness of 20 nm.
  • This transparent support substrate was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus, and each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with a constituent material of each layer in an amount optimal for device fabrication.
  • the evaporation crucible a crucible made of a resistance heating material made of molybdenum or tungsten was used.
  • ⁇ -NPD was deposited on the hole injection layer at a deposition rate of 0.1 nm / second to form a hole transport layer having a layer thickness of 40 nm.
  • MCP as the host compound (B) and TBPe as the dopant (A) were co-deposited at a deposition rate of 0.1 nm / second so as to be 94% and 6% by volume, respectively, to form a light emitting layer having a layer thickness of 30 nm. .
  • TPBi (1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene) was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a layer thickness of 30 nm. Furthermore, after forming sodium fluoride with a film thickness of 1 nm, 100 nm of aluminum was vapor-deposited to form a cathode. The non-light-emitting surface side of the above element was covered with a can-shaped glass case in an atmosphere of high purity nitrogen gas with a purity of 99.999% or more, and an electrode lead-out wiring was installed to prepare an organic EL element 4-1.
  • organic EL element 4-3 (Preparation of organic EL element 4-3) The light emitting layer was formed so that the host compound (B) was mCP, the dopant (A) was TBPe, and the combined compound (C) was the comparative compound 4, and the respective ratios were 79%, 6%, and 15% by volume.
  • An organic EL element 4-3 was produced in the same manner as in the production of the organic EL element 4-1, except for the above.
  • the organic EL device 4 was prepared in the same manner as the organic EL device 4-3, except that the host compound (B), dopant (A), and combination compound (C) in the light emitting layer and the ratio thereof were changed as shown in Table 4. -4 to 4-7 were prepared.
  • the luminous efficiency of each sample when driving the organic EL element was evaluated by performing the following measurements. For each sample, the emission luminance of each sample was measured at room temperature (about 25 ° C.) using a spectral radiance meter CS-2000 (manufactured by Konica Minolta), and the initial emission efficiency at an emission luminance of 3000 cd / m 2 was determined. Asked. The evaluation value of luminous efficiency was calculated by the following formula.
  • Luminous efficiency (relative value) (luminous efficiency at luminous luminance 3000 cd / m 2 / organic EL element 4-1 luminous efficiency at luminous luminance 3000 cd / m 2 ) ⁇ 100
  • Table 4 shows the obtained results. Table 4 shows that the element is driven with lower power as the relative value of the luminous efficiency is larger.
  • the driving voltage of each sample at the time of driving the organic EL element was evaluated by performing the following measurement. Measurement of initial driving voltage For each sample, the emission luminance of each sample was measured at room temperature (about 25 ° C.) using a spectral radiance meter CS-2000 (manufactured by Konica Minolta), and the emission luminance was 1000 cd / m. The initial drive voltage in 2 was obtained.
  • the organic EL elements 4-4 to 4-7 have higher luminous efficiency than the comparative element. This is considered to be an effect that the ⁇ -conjugated compound according to the present invention assists light emission of other fluorescent compounds. That is, when the ⁇ -conjugated compound according to the present invention, which has a higher energy level than the luminescent material, is excited in the light emitting device, the luminescent material efficiently receives the energy, so that the ⁇ -conjugated compound according to the present invention itself It is considered that luminous efficiency comparable to that of light emission can be obtained.
  • the present invention is suitable for providing an organic electroluminescence device having a high fluorescence quantum yield and excellent luminous efficiency. Moreover, it is suitable for providing the fluorescent compound used for the said organic electroluminescent element, the luminescent thin film containing the said fluorescent compound, the display apparatus provided with the said organic electroluminescent element, and an illuminating device.

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  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

La présente invention aborde le problème de la réalisation d'un élément électroluminescent organique qui présente un rendement quantique de fluorescence élevé et aussi de la réalisation d'un composé émetteur de lumière fluorescente utilisé dans l'élément électroluminescent organique, d'un film mince émetteur de lumière contenant le composé émetteur de lumière fluorescente, ainsi que d'un dispositif d'affichage et d'un dispositif d'éclairage équipés de l'élément électroluminescent organique ou du film mince émetteur de lumière. L'élément électroluminescent organique possède une couche organique qui comprend au moins une couche émettrice de lumière entre une cathode et une anode. L'élément électroluminescent organique est caractérisé en ce que l'au moins une couche émettrice de lumière possède une structure spécifique et contient un composé conjugué π pour lequel la valeur absolue (ΔEst) de la différence d'énergie entre l'état de singulet excité minimal et l'état de triplet excité minimal est inférieure ou égale à 0,5 eV.
PCT/JP2015/071618 2014-07-31 2015-07-30 Élément électroluminescent organique, dispositif d'affichage, dispositif d'éclairage, composé émetteur de lumière fluorescente, et film mince émetteur de lumière WO2016017741A1 (fr)

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WO2016181844A1 (fr) * 2015-05-08 2016-11-17 コニカミノルタ株式会社 Composé pi-conjugué, corps fluorescent retardé, film mince électroluminescent, élément électroluminescent organique, dispositif d'affichage et dispositif d'éclairage
JP2017152585A (ja) * 2016-02-25 2017-08-31 株式会社ジャパンディスプレイ 有機エレクトロルミネッセンス表示装置用材料及び有機エレクトロルミネッセンス表示装置
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CN110577513A (zh) * 2019-08-28 2019-12-17 武汉华星光电半导体显示技术有限公司 电致发光材料、电致发光材料的制备方法及发光器件
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CN110642820A (zh) * 2019-09-04 2020-01-03 武汉华星光电半导体显示技术有限公司 电子阻挡材料及有机电致发光器件
CN110627821A (zh) * 2019-09-29 2019-12-31 上海天马有机发光显示技术有限公司 一种化合物、有机电致发光器件、显示面板及显示装置
US11957043B2 (en) 2020-05-06 2024-04-09 Samsung Display Co., Ltd. Light-emitting device and electronic apparatus comprising same
WO2023048534A1 (fr) * 2021-09-27 2023-03-30 솔루스첨단소재 주식회사 Composé organique et dispositif électroluminescent organique l'utilisant

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