WO2016017684A1 - Matériau d'élément électroluminescent organique, élément électroluminescent organique, film mince émettant de la lumière, dispositif d'affichage et dispositif d'éclairage - Google Patents

Matériau d'élément électroluminescent organique, élément électroluminescent organique, film mince émettant de la lumière, dispositif d'affichage et dispositif d'éclairage Download PDF

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WO2016017684A1
WO2016017684A1 PCT/JP2015/071483 JP2015071483W WO2016017684A1 WO 2016017684 A1 WO2016017684 A1 WO 2016017684A1 JP 2015071483 W JP2015071483 W JP 2015071483W WO 2016017684 A1 WO2016017684 A1 WO 2016017684A1
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ring
group
organic
compound
light
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康生 宮田
池水　大
北　弘志
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コニカミノルタ株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/167—Electron transporting layers between the light-emitting layer and the anode
    • 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

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  • the present invention relates to an organic electroluminescent element material, an organic electroluminescent element using the organic electroluminescent element material, a light-emitting thin film, and a display device and an illumination device provided with the organic electroluminescent element. More specifically, the present invention relates to an organic electroluminescence element with improved luminous efficiency.
  • 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 element emission methods There are two types of organic EL element emission methods: “phosphorescence emission” that emits light when returning from the excited triplet state to the ground state and “fluorescence emission” that emits light when returning from the excited singlet state to the ground state. There is a street.
  • TTA triplet-triplet annihilation
  • TTF Triplet-Triplet Fusion
  • thermoally activated delayed fluorescence also referred to as “thermally excited delayed fluorescence”: Thermally Activated Delayed Fluorescence (hereinafter abbreviated as “TADF” where appropriate)
  • TADF Thermally Activated Delayed Fluorescence
  • ⁇ Est In order to minimize ⁇ Est in an organic compound, it is desirable to localize without mixing the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the molecule.
  • HOMO highest occupied molecular orbital
  • LUMO lowest unoccupied molecular orbital
  • FIG. 1A and 1B are schematic diagrams showing energy diagrams of a compound that expresses a TADF phenomenon (TADF compound) and a general fluorescent compound.
  • TADF compound TADF compound
  • FIG. 1A HOMO is localized at the 1st and 2nd carbazolyl groups on the benzene ring, and LUMO is localized at the 4th and 5th cyano groups. Therefore, HOMO and LUMO of 2CzPN can be separated, ⁇ Est becomes extremely small and TADF phenomenon appears.
  • 2CzXy FIG.
  • the present invention has been made in view of the above-described problems and situations, and a problem to be solved is to provide a new organic electroluminescence device with improved luminous efficiency.
  • Another object of the present invention is to provide an organic electroluminescent element material used for the organic electroluminescent element, a light-emitting thin film containing the organic electroluminescent element material, and a display device and an illumination device including the organic electroluminescent element. .
  • the present inventor performs a molecular design in which the ⁇ -conjugated plane having an electron-donating group and the ⁇ -conjugated plane having an electron-withdrawing group are twisted by 45 degrees or more. As a result, it was found that HOMO and LUMO can be effectively separated, and the TADF phenomenon can be further expressed, and the present invention has been achieved.
  • An organic electroluminescence device having at least one light emitting layer between an anode and a cathode, wherein at least one layer of the light emitting layer contains a ⁇ -conjugated compound having a structure represented by the following general formula (1)
  • the ⁇ -conjugated compound is formed from the surface of the ring structure A bonded to the nitrogen atom, the nitrogen atom, the carbon atom, and X.
  • An organic electroluminescence device characterized in that an angle ⁇ formed with a plane of the ring structure is within a range of 45 to 90 degrees.
  • A represents a group having a ring structure
  • A represents an aryl group substituted with an electron-withdrawing group, or an optionally substituted heteroaryl group.
  • B and C may be a single ring or X represents O, S, N—R 1 , C—R 2 (R), which is composed of a condensed ring structure of up to three rings, and each independently represents an optionally substituted aryl ring or heteroaryl ring. 3 ), Si—R 4 (R 5 ), B—R 6 or a single bond, wherein R 1 to R 6 are each independently a hydrogen atom, an alkyl group, an aryl group, Represents a heteroaryl group.) 2.
  • B and C are each independently substituted, benzene ring, naphthalene ring, indene ring, benzosilole ring, indole ring, benzofuran ring, benzothiophene ring, thienothiophene ring, phenanthrene ring, fluorene ring,
  • the organic electroluminescence device according to any one of Items 1 to 3, which represents a dibenzosilol ring, a dibenzoborol ring, a carbazole ring, a dibenzofuran ring, or a dibenzothiophene ring.
  • the ⁇ -conjugated compound having a structure represented by the general formula (1) is a ⁇ -conjugated compound having a structure represented by any of the following general formulas (2) to (15) The organic electroluminescent element according to any one of items 1 to 4.
  • a and X have the same meanings as A and X in the general formula (1).
  • Y represents O, S, N—R 7 , C—R 8 (R 9 ), Si—R 10 (R 11 ), B—R 12 or CH ⁇ CH, R 7 to R 12 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, each of which may be substituted. 6).
  • Item 6 The organic electroluminescence device according to Item 5, wherein the ring structure A described in the general formulas (1) to (15) is a group represented by the following general formulas (16) to (27) .
  • R 13 ⁇ R 17 each independently represent a hydrogen atom, a cyano group or a nitrogen-containing aromatic ring as the aryl group or an electron withdrawing group substituted with an electron withdrawing group, R 13 ⁇ R 17 At least one of them represents an aryl group substituted with an electron-withdrawing group or a cyano group or a nitrogen-containing aromatic ring as an electron-withdrawing group, provided that [R 13 and R 17 ] are simultaneously a hydrogen atom. Absent.
  • R 18 to R 33 , R 35 to R 37 , R 39 to R 40 , R 42 to R 43 , R 45 , R 47 and R 49 may each independently be a hydrogen atom or a cyano group, Represents an aryl ring or a heteroaryl ring, provided that [R 18 and R 21 ], [R 22 and R 25 ], [R 26 and R 28 ], [R 29 and R 31 ] or [R 32 and R 33 ] is not simultaneously a hydrogen atom.
  • R 34 , R 38 , R 41 , R 44 , R 46 and R 48 each represent a cyano group, an aryl ring or a heteroaryl ring, each of which may be substituted.
  • a wavy line represents a coupling point. ) 7).
  • the R 1 in the general formula (1) is a group represented by the general formulas (16) to (27), according to any one of the first to sixth items, Organic electroluminescence device.
  • the ⁇ -conjugated compound having the structure represented by the general formula (1) is a structure represented by the general formulas (2) to (15), and the ring structure A is represented by the general formulas (16) to (27).
  • X represents O, C—R 2 (R 3 ), Si—R 4 (R 5 ), or a single bond, and R 2 to R 5 are each independently substituted
  • Y represents O, N—R 7 , C—R 8 (R 9 ), Si—R 10 (R 11 ) or CH ⁇ CH
  • R 7 is Represents an optionally substituted aryl group or a group represented by the general formulas (16) to (27), and R 8 to R 11 each represents an optionally substituted alkyl group or an aryl ring.
  • Item 7 The organic electroluminescence device according to item 6, wherein:
  • the absolute value ( ⁇ Est) of the difference between the lowest excited singlet energy level and the lowest excited triplet energy level of the ⁇ -conjugated compound having the structure represented by the general formula (1) is 0.5 eV or less. 10.
  • the light emitting layer contains a ⁇ -conjugated compound having a structure represented by the general formula (1) and at least one of a fluorescent compound and a phosphorescent compound.
  • Item 10 The organic electroluminescence device according to any one of Items 10 to 10.
  • the light emitting layer contains a ⁇ -conjugated compound having a structure represented by the general formula (1), at least one of a fluorescent compound and a phosphorescent compound, and a host compound.
  • the organic electroluminescent element according to any one of items 1 to 11 described above.
  • a ⁇ -conjugated compound having a structure represented by the following general formula (1) is contained, and the ⁇ -conjugated compound is bonded to a nitrogen atom in each of a ground state, a lowest excited singlet state, and a lowest excited triplet state.
  • A represents a group having a ring structure
  • A represents an aryl group substituted with an electron-withdrawing group, or an optionally substituted heteroaryl group.
  • B and C may be a single ring or X represents O, S, N—R 1 , C—R 2 (R), which is composed of a condensed ring structure of up to three rings, and each independently represents an optionally substituted aryl ring or heteroaryl ring.
  • a display device comprising the organic electroluminescence element according to any one of items 1 to 12.
  • An organic electroluminescence element according to any one of items 1 to 12 is provided.
  • the angle ⁇ formed by the surface of the ring structure A bonded to the nitrogen atom and the surface of the ring structure composed of the nitrogen atom, carbon atom and X is in the range of 45 to 90 degrees.
  • A represents a group having a ring structure
  • A represents an aryl group substituted with an electron-withdrawing group, or an optionally substituted heteroaryl group.
  • B and C may be a single ring or X represents O, S, N—R 1 , C—R 2 (R), which is composed of a condensed ring structure of up to three rings, and each independently represents an optionally substituted aryl ring or heteroaryl ring. 3 ), Si—R 4 (R 5 ), B—R 6 or a single bond, wherein R 1 to R 6 are each independently a hydrogen atom, an alkyl group, an aryl group, Represents a heteroaryl group.
  • the above-mentioned means of the present invention can provide a new organic electroluminescence device that realizes an improvement in luminous efficiency.
  • the organic electroluminescent element material used for the said organic electroluminescent element, the luminescent thin film containing this organic electroluminescent element material, the display apparatus provided with the said organic electroluminescent element, and an illuminating device can be provided. .
  • the ⁇ -conjugated compound according to the present invention is characterized in that the structural change between the ground state (S 0 ) and the excited state (S 1 and T 1 ) is small.
  • the structural change between the ground state (S 0 ) and the excited state (S 1 and T 1 ) is small.
  • the molecule when a molecule is in an excited state from a ground state, the molecule has a high energy state, so that the structure of the molecule changes in order to obtain a more stable structure.
  • a molecular design has been found in which a ⁇ -conjugated plane having an electron-donating group and a ⁇ -conjugated plane having an electron-withdrawing group maintain a structure that is twisted 45 degrees or more even in the ground state and the excited state.
  • the structural change between the ground state and the excited state is small, the consumption of exciton energy can be suppressed, so that the light emission efficiency is considered to be improved.
  • Schematic diagram showing energy diagram of TADF compound Schematic diagram showing the energy diagram of a general fluorescent compound
  • 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
  • the angle ⁇ is in the range of 75 to 90 degrees in the ground state from the viewpoint of manifesting the effects of the present invention. Furthermore, it is preferable that the angle ⁇ is in the range of 75 to 90 degrees in the lowest excited singlet state and the lowest excited state, because the effect of increasing the light emission efficiency is obtained.
  • the above B and C are each independently substituted, benzene ring, naphthalene ring, indene ring, benzosilol ring, indole ring, benzofuran ring, benzothiophene ring, thienothiophene ring.
  • Phenanthrene ring, fluorene ring, dibenzosilol ring, dibenzoborol ring, carbazole ring, dibenzofuran ring or dibenzothiophene ring is independently substituted, benzene ring, naphthalene ring, indene ring, benzosilol ring, indole ring, benzofuran ring, benzothiophene ring, thienothiophene ring.
  • the ⁇ -conjugated compound having the structure represented by the general formula (1) is a ⁇ -conjugated compound having a structure represented by any one of the general formulas (2) to (15). This is preferable from the viewpoint of expression of the crossing phenomenon.
  • the ring structure A described in the general formulas (1) to (15) is preferably a group represented by the general formulas (16) to (27) from the viewpoint of high luminous efficiency.
  • R 1 in the general formula (1) is preferably a group represented by the general formulas (16) to (27).
  • ring structure A is a structure represented by general formulas (16) to (27)
  • X is O, C—R 2 (R 3 ), Si—R 4 (R 5 ) or a single bond
  • R 2 to R 5 each independently represents an optionally substituted alkyl group or an optionally substituted aryl ring
  • Y represents O , N—R 7 , C—R 8 (R 9 ), Si—R 10 (R 11 ) or CH ⁇ CH, wherein R 7 is an aryl group which may be substituted or the above general formula (16) to represents a group represented by (27), R 8 ⁇ R 11 may be each substituted, preferred to represent an alkyl
  • the absolute value ( ⁇ Est) of the difference between the lowest excited singlet energy level and the lowest excited triplet energy level of the ⁇ -conjugated compound having the structure represented by the general formula (1) is 0.5 eV or less. Is preferable from the viewpoint of high luminous efficiency.
  • the light emitting layer includes a ⁇ -conjugated compound having a structure represented by the general formula (1), and at least one of a fluorescent compound and a phosphorescent compound. It is preferable to contain. Furthermore, in the present invention, the light-emitting layer includes a ⁇ -conjugated compound having a structure represented by the general formula (1), at least one of a fluorescent compound and a phosphorescent compound, and a host compound It is preferable to contain. Thereby, the effect of high luminous efficiency is obtained. Moreover, the organic electroluminescent element material containing the (pi) conjugated compound which has a structure represented by the said General formula (1), and light emission containing this (pi) conjugated compound Can be used as a conductive thin film.
  • the organic EL element of the present invention can be suitably provided in a lighting device and a display device.
  • Organic EL emission methods There are two types of organic EL emission methods: “phosphorescence emission” that emits light when returning from the excited triplet state to the ground state and “fluorescence emission” that emits light when returning from the excited singlet state to the ground state. is there.
  • TTA triplet-triplet annihilation
  • 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.
  • a rare 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.
  • TTA triplet-triplet annihilation
  • Fluorescent compounds have the advantage of infinite molecular design as described above. That is, among the molecularly designed compounds, there are compounds in which the energy level difference between the excited triplet state and the excited singlet state is extremely close.
  • HOMO is distributed in electron donating sites and LUMO is distributed in electron withdrawing sites in the electron orbit of the molecule.
  • LUMO is distributed in electron withdrawing sites in the electron orbit of the molecule.
  • 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 the rings in the molecule or by introducing a condensed ring with a large ⁇ conjugate plane. means.
  • the electronic state of the molecule is a donor / acceptor type molecule in which the HOMO and LUMO sites are separated. It becomes a state close to the inner CT (intramolecular charge transfer state).
  • stabilization is achieved by bringing the donor part of one molecule and the acceptor part of the other molecule close to each other.
  • a stabilization state is not limited to the formation between two molecules, but can also be formed between a plurality of molecules such as three or five molecules.
  • various stabilization states with a wide distribution are obtained.
  • the shape of the absorption spectrum and emission spectrum becomes broad.
  • various existence states can be taken depending on the direction and angle of interaction between the two molecules.
  • the shape of the emission spectrum becomes broad.
  • the broad emission spectrum causes two major problems.
  • One problem is that the color purity of the emitted color is lowered. This is not a big problem when applied to lighting applications, but when used for electronic displays, the color gamut is small and the color reproducibility of pure colors is low. It becomes difficult.
  • the phosphorescent 0-0 band derived from T 1 having energy lower than that of S 1 is also shortened (increased T 1 ). Therefore, the compound used for the host compound needs to have a high S 1 and a high T 1 in order to prevent reverse energy transfer from the dopant.
  • a host compound consisting essentially of an organic compound takes a plurality of active and unstable chemical species such as a cation radical state, an anion radical state, and an excited state in an organic EL device.
  • active and unstable chemical species such as a cation radical state, an anion radical state, and an excited state in an organic EL device.
  • 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 by molecular orbital calculation.
  • structure optimization and calculation of electron density distribution by molecular orbital calculation of ⁇ -conjugated compounds in the present invention are performed using molecular orbital calculation software using B3LYP as a functional and 6-31G (d) as a basis function as a calculation method.
  • B3LYP molecular orbital calculation software
  • 6-31G (d) 6-31G
  • the lowest excited singlet energy level S 1 of the ⁇ -conjugated compound in the present invention is defined in the present invention as calculated in the same manner as in a normal method. That is, a sample to be measured is deposited on a quartz substrate to prepare a sample, and the absorption spectrum (vertical axis: absorbance, horizontal axis: wavelength) of this sample is measured at room temperature (300 K). A tangent line is drawn with respect to the rising edge of the absorption spectrum on the long wavelength side, and is calculated from a predetermined conversion formula based on the wavelength value at the intersection of the tangent line and the horizontal axis.
  • the molecules themselves of the ⁇ -conjugated compound used in the present invention have a relatively high aggregation property, an error due to aggregation may occur in the measurement of the thin film.
  • the lowest excited singlet energy level S 1 in the present invention is room temperature (25 ° C.
  • the peak value of the maximum emission wavelength in the solution state of the ⁇ -conjugated compound in (1) was used as an approximate value.
  • the organic EL device of the present invention is an organic electroluminescence device having at least one light emitting layer between an anode and a cathode, wherein at least one layer of the light emitting layer is represented by the general formula (1).
  • a surface of the ring structure A bonded to a nitrogen atom in each of the ground state, the lowest excited singlet state, and the lowest excited triplet state, and a ⁇ -conjugated compound having An angle ⁇ formed with a plane of a ring structure composed of atoms, carbon atoms and X is in the range of 45 to 90 degrees.
  • Anode / light emitting layer // cathode Anode / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / cathode (4) Anode / hole transport layer / light emitting layer / Electron transport layer / cathode (5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode (7) Anode / hole injection layer / hole transport layer / (electron blocking layer /) light emitting layer / (hole blocking layer /) electron transport layer / electron injection layer / cathode Among the above, the configuration of (7) is Although used preferably, it is
  • 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 layer excluding the anode and the cathode is also referred to as “organic layer”.
  • 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.
  • 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 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. From the viewpoint, it is preferably adjusted to a range of 2 nm to 5 ⁇ m, more preferably adjusted to a range of 2 to 500 nm, and further preferably adjusted to a range of 5 to 200 nm.
  • each light emitting layer used in the present invention is preferably adjusted to a range of 2 nm to 1 ⁇ m, more preferably adjusted to a range of 2 to 200 nm, and further preferably in a range of 3 to 150 nm. Adjusted.
  • the light-emitting layer used in the present invention contains a light-emitting dopant (light-emitting compound, light-emitting dopant, also simply referred to as a dopant), and further the above-described host compound (also referred to as matrix material, light-emitting host compound, or simply host). It is preferable to contain.
  • a light-emitting dopant light-emitting compound, light-emitting dopant, also simply referred to as a dopant
  • host compound also referred to as matrix material, light-emitting host compound, or simply host. It is preferable to contain.
  • the luminescent dopant As the luminescent dopant, a fluorescent luminescent dopant (also referred to as a fluorescent luminescent compound or a fluorescent dopant), a delayed fluorescent luminescent dopant, or a phosphorescent luminescent dopant (also referred to as a phosphorescent luminescent compound or a phosphorescent dopant). .) Is preferably used.
  • the light-emitting layer contains the ⁇ -conjugated compound according to the present invention as a fluorescent light-emitting compound or an assist dopant in a range of 0.1 to 50% by mass, particularly in a range of 1 to 30% by mass. It is preferable to contain within.
  • the luminescent compound used in the present invention may be used in combination of two or more kinds, a combination of fluorescent luminescent compounds having different structures, or a combination of a fluorescent luminescent compound and a phosphorescent luminescent compound. May be. Thereby, arbitrary luminescent colors can be obtained.
  • An absolute value ( ⁇ Est) of a difference between the lowest excited singlet energy level and the lowest excited triplet energy level is 0.5 eV or less, a luminescent compound, and a host compound.
  • ⁇ Est an absolute value of a difference between the lowest excited singlet energy level and the lowest excited triplet energy level.
  • 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 energy levels of S 1 and T 1 of the ⁇ -conjugated compound are S of the host compound. 1 and T 1 of the lower than the energy level, it is preferably higher than the energy level of the S 1 and T 1 of the light-emitting compound.
  • the light emitting layer has a mass ratio of 0.1 to 50% of the fluorescent compound and / or phosphorescent compound with respect to the ⁇ -conjugated compound. It is preferable to contain.
  • the emission spectrum of the ⁇ -conjugated compound according to the present invention and the absorption spectrum of the luminescent compound preferably overlap.
  • 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.
  • one or a plurality of light-emitting layers contain a plurality of light-emitting dopants having different emission colors and emit white light.
  • the ⁇ -conjugated compound according to the present invention is converted into a singlet exciton by reverse intersystem crossing (RISC) without deactivating the triplet exciton generated on the ⁇ -conjugated compound in the light emitting layer.
  • RISC reverse intersystem crossing
  • It is a compound having a function of improving luminous efficiency as an assist dopant, a host compound, and a fluorescent dopant, which improves luminous efficiency by suppressing deactivation of the element, and can be preferably used as an organic EL device material.
  • the ⁇ -conjugated compound according to the present invention is characterized in that the structural change between the ground state (S 0 ) and the excited state (S 1 and T 1 ) is small.
  • the structural change between the ground state (S 0 ) and the excited state (S 1 and T 1 ) is small.
  • the molecule when a molecule is in an excited state from a ground state, the molecule has a high energy state, so that the structure of the molecule changes in order to obtain a more stable structure.
  • the present application has found a molecular design that maintains a structure in which the ⁇ -conjugated plane having an electron-donating group and the ⁇ -conjugated plane having an electron-withdrawing group are twisted by 45 degrees or more even in an excited state.
  • the structural change between the ground state and the excited state is small, the consumption of exciton energy can be suppressed, so that the light emission efficiency is considered to be improved.
  • the twist angle of the ⁇ -conjugated compound having such a twisted structure is such that the plane of the ring structure A bonded to the nitrogen atom and the plane of the ring structure consisting of the nitrogen atom, carbon atom and X And can be measured as follows.
  • the structure of the ground state, the excited singlet state, and the excited triplet state is optimized using the above theoretical calculation, and the angle ⁇ is calculated using these optimized structures.
  • the angle ⁇ is defined as “the carbon atom adjacent to the condensed ring structure B or C bonded to the nitrogen atom described in the general formula (1)”, “the nitrogen atom described in the general formula (1)”, and “the general formula A plane consisting of three atoms, “a nitrogen atom in ring structure A in which the nitrogen atom described in (1) and ring structure A are bonded”, and “a nitrogen atom described in general formula (1)” and “general formula The atom in ring structure A in which the nitrogen atom described in (1) is bonded to ring structure A ”and“ the atom in ring structure A in which the nitrogen atom described in general formula (1) is bonded to ring structure A ” It can be calculated by selecting the atoms so that the angle formed by the two planes of the plane consisting of the three atoms “the atoms in the ring structure A bonded to the
  • a functional B3LYP and a basis function 6-31G are obtained by molecular orbital calculation software Gaussian09 (Revision C.01, MJ Frisch, et al, Gaussian, Inc., 2010.).
  • a ground state structure can be obtained by performing a density functional calculation using (d).
  • the structures of the lowest excited singlet state and the lowest excited triplet state can be obtained by performing a calculation by the time-dependent density functional method (Time-Dependent DFT) using the functional B3LYP and the basis function 6-31G (d). it can.
  • the angle ⁇ can be expressed as “the carbon atom adjacent to the condensed ring structure B or C bonded to the nitrogen atom described in the general formula (1)” and “the general formula (1).
  • A represents a group having a ring structure
  • A represents an aryl group substituted with an electron-withdrawing group, or an optionally substituted heteroaryl group.
  • B and C each represent an aryl ring or a heteroaryl ring that is composed of a monocyclic ring structure or a condensed ring structure of up to three rings, and each may be independently substituted.
  • X represents O, S, N—R 1 , C—R 2 (R 3 ), Si—R 4 (R 5 ), B—R 6 or a single bond.
  • R 1 to R 6 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, each of which may be substituted.
  • A represents a group having a ring structure, and A represents an aryl group substituted with an electron-withdrawing group, or an optionally substituted heteroaryl group.
  • an aryl ring having 6 to 20 carbon atoms is preferable.
  • a benzene ring, naphthalene ring, fluorene ring, phenanthrene ring, anthracene ring, biphenylene ring, chrysene ring, pyrene ring, triphenylene ring, chrysene ring, fluoranthene ring, perylene ring, biphenyl ring, and terphenyl ring are more preferable.
  • Particularly preferred are a benzene ring, a biphenyl ring and a terphenyl ring.
  • This electron ring has an electron-withdrawing substituent.
  • the electron withdrawing property refers to the property of decreasing the electron density at a specific position of the molecule, and the electron withdrawing property means a substituent having such properties.
  • Specific examples of the electron-withdrawing substituent include heteroaryl groups such as nitrogen-containing heteroaryl groups, halogen atoms such as fluorine atoms, acyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and cyano groups.
  • An aryl group or a heteroaryl group is preferred as the group substituted for the heteroaryl group.
  • Examples of the aryl group and heteroaryl group include the same aryl groups and heteroaryl groups that constitute the ring structure A.
  • the alkyl group may be linear, branched, or cyclic, and examples thereof include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, and n- Propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group Group, 2-hexyloctyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-
  • Methyl group, ethyl group, isopropyl group, t-butyl group, cyclohexyl group, 2- Ethylhexyl group, 2-hexyl octyl group are preferable.
  • the alkoxy group may be either a straight chain or a branched chain, and examples thereof include a linear or branched alkoxy group having 1 to 20 carbon atoms. Specific examples include a methoxy group, an ethoxy group, n- Propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyl Oxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group 2-n-hexyl-n-octy
  • An octyloxy group is preferred.
  • A is an aryl ring having 6 to 20 carbon atoms substituted with 1 to 5 cyano groups, an aryl ring having 6 to 20 carbon atoms substituted with 1 to 5 fluorine atoms, An aryl ring having 6 to 20 carbon atoms substituted with 1 to 5 fluoroalkyl groups, a benzene ring substituted with an optionally substituted nitrogen-containing heteroaryl ring, or an optionally substituted nitrogen-containing aroma A ring is preferred.
  • B and C each represent an aryl ring or a heteroaryl ring that is composed of a monocyclic ring structure or a condensed ring structure of up to three rings, and each may be independently substituted.
  • B and C are each independently substituted, benzene ring, naphthalene ring, indene ring, benzosilole ring, indole ring, benzofuran ring, benzothiophene ring, thienothiophene ring, phenanthrene ring, fluorene ring, dibenzo It preferably represents a silole ring, dibenzoborol ring, carbazole ring, dibenzofuran ring or dibenzothiophene ring.
  • X represents O, S, N—R 1 , C—R 2 (R 3 ), Si—R 4 (R 5 ), B—R 6 or a single bond.
  • C—R 2 (R 3 ) represents a divalent group in which two groups of R 2 and R 3 are substituted on a carbon atom.
  • R 1 to R 6 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, each of which may be substituted. Examples of the alkyl group include the same aryl group and heteroaryl group as the aryl group and heteroaryl group constituting the ring structure A.
  • R 1 is preferably a group represented by the following general formulas (16) to (27).
  • the ⁇ -conjugated compound having a structure represented by the general formula (1) is preferably a ⁇ -conjugated compound having a structure represented by any of the following general formulas (2) to (15).
  • a and X have the same meanings as A and X in the general formula (1).
  • Y represents O, S, N—R 7 , C—R 8 (R 9 ), Si—R 10 (R 11 ), B—R 12 or CH ⁇ CH, each of R 7 to R 12 independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, each of which may be substituted.
  • R 7 to R 12 are the same groups as R 1 to R 6 described for X in the general formula (1), and R 7 is represented by the general formulas (16) to (27) described later. It is preferable that it is a group.
  • the ring structure A described in the general formulas (1) to (15) is preferably a group represented by the following general formulas (16) to (27).
  • R 13 ⁇ R 17 each independently represent a hydrogen atom, a cyano group or a nitrogen-containing aromatic ring as the aryl group or an electron withdrawing group substituted with an electron withdrawing group
  • the R 13 ⁇ R 17 At least one of them represents an aryl group substituted with an electron-withdrawing group or a cyano group or a nitrogen-containing aromatic ring as an electron-withdrawing group.
  • [R 13 and R 17 ] are not simultaneously hydrogen atoms. The same thing as the above-mentioned is mentioned as a nitrogen-containing aromatic ring.
  • R 18 to R 33 , R 35 to R 37 , R 39 to R 40 , R 42 to R 43 , R 45 , R 47 and R 49 may each independently be a hydrogen atom or a cyano group, Represents an aryl ring or a heteroaryl ring, provided that [R 18 and R 21 ], [R 22 and R 25 ], [R 26 and R 28 ], [R 29 and R 31 ] or [R 32 and R 33 ] is not simultaneously a hydrogen atom.
  • R 34 , R 38 , R 41 , R 44 , R 46 and R 48 each represent a cyano group, an aryl ring or a heteroaryl ring, each of which may be substituted.
  • a wavy line represents a coupling point.
  • aryl group and heteroaryl group examples include the same aryl groups and heteroaryl groups that constitute the ring structure A.
  • the ring structure A is a group represented by the general formulas (16) to (27), the ring structure A is bonded to the nitrogen atom, and the ring structure consisting of a nitrogen atom, a carbon atom, and X
  • the angle ⁇ formed with the surface can be increased to facilitate separation of HOMO and LUMO.
  • the ⁇ -conjugated compound of the present invention suppresses exciton energy consumption because ⁇ Est is minimized by effective separation of HOMO and LUMO and the structural change between the ground state and the excited state is small. Therefore, it can be used as a compound suitable for hole transport and electron transport. Therefore, the ⁇ -conjugated compound of the present invention is not limited to use only in the light emitting layer, and the above-described hole injection layer, hole transport layer, electron blocking layer, hole blocking layer, electron transport layer, electron injection layer And may be used for an intermediate layer or the like.
  • the firefly ⁇ -conjugated compound is described in, for example, the method described in International Publication No. 2011/055933, International Publication No. 2011/132866 and International Publication No. 2012/035853, or the references described in these references. It can be synthesized by referring to the method.
  • (1.2) Fluorescent Luminescent Dopant As the fluorescent luminescent dopant (fluorescent dopant), the ⁇ -conjugated compound of the present invention may be used, or a known fluorescent dopant or delayed fluorescence used in the light emitting layer of the organic EL device. You may use it, selecting suitably from sex dopant.
  • 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 phosphorescent 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 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 compounds may be used alone or in combination of two or more. 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 ⁇ -conjugated compound used in the present invention may be used as described above, but there is no particular limitation. From the viewpoint of reverse energy transfer, those having an excitation energy larger than the excitation singlet energy of the dopant are preferred, and those having an excitation triplet energy larger than the excitation triplet energy of the dopant are more preferred.
  • the existence of the excited triplet state of the TADF compound is long, so that the T 1 energy level of the host compound itself is high, and the host compounds are associated with each other.
  • Molecules in which the host compound does not decrease in T 1 such as not forming a low T 1 state in that state, the 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 of the structure is required.
  • the host compound itself needs to have high electron hopping mobility, high hole hopping movement, and small structural change when it enters the excited triplet state. It is.
  • Preferred examples of host compounds that satisfy such requirements include those having a high T 1 energy level such as a carbazole skeleton, an azacarbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, or an azadibenzofuran skeleton.
  • 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 element driving. From the viewpoint of operation, it is preferable to have a high glass transition temperature (Tg). Tg is preferably 90 ° C. or higher, more preferably 120 ° C. or higher.
  • the host compound used in the present invention it is also preferable to use the ⁇ -conjugated compound according to the present invention as described above.
  • the ⁇ -conjugated compound according to the present invention has a condensed ring structure, so that a ⁇ electron cloud spreads, the carrier transport property is high, and the glass transition temperature (Tg) is high.
  • the ⁇ -conjugated compound according to the present invention has a high T 1 and can be suitably used for a light-emitting material having a short emission wavelength (that is, a high T 1 and S 1 ).
  • 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. When light is reflected by the cathode, this interference effect can be efficiently utilized by appropriately adjusting the total thickness of the electron transport layer between several nanometers and several micrometers.
  • 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.
  • 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.
  • a polymer material in which these materials are introduced into a polymer chain or these materials as a polymer main chain can 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 known 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, aza Examples thereof include dibenzofuran derivatives, azadibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, and benzimidazole derivatives.
  • 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.
  • 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 As 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.
  • the materials used for the electron injection layer may be used alone or in combination of two or more.
  • 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 5 nm to 5 ⁇ m, more preferably 5 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.
  • 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 a hole transport material.
  • 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.
  • the above-described configuration of the hole transport layer 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 As 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.
  • Examples of materials used for the hole injection layer include: Examples thereof include materials used for the above-described hole transport layer.
  • phthalocyanine derivatives typified by copper phthalocyanine, hexaazatriphenylene derivatives, metal oxides typified by vanadium oxide, amorphous carbon as described in JP-T-2003-519432, 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.
  • additives include halogen elements and halogenated compounds such as bromine, iodine and chlorine, alkali metals and alkaline earth metals such as Pd, Ca, and Na, 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. .
  • ⁇ Method for forming organic layer> 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, intermediate layer, etc.) according to the present invention will be described.
  • the formation method of the organic layer according to the present invention is not particularly limited, and a conventionally known formation method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used.
  • wet method examples 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 be dispersed by a dispersion method such as ultrasonic wave, high shearing force dispersion or media dispersion.
  • 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 it is preferable to consistently produce from the hole injection layer to the cathode by one evacuation, but it may be taken out halfway and subjected to different film forming 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.
  • an electrode substance include metals such as Au, 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.
  • the anode may be formed by depositing a thin film of these electrode materials by vapor deposition or sputtering, and a pattern having a desired shape may be formed by photolithography, or when pattern accuracy is not so high (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.
  • a wet film forming method such as a printing method or a coating method can 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.
  • 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 improved, which is convenient.
  • 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 or a substrate) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic and the like, and is transparent or opaque. May be.
  • the support substrate is preferably transparent.
  • 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 polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by J
  • 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 oxygen permeability measured by a method according to JIS K 7126-1987.
  • it is preferably a high-barrier film having 1 ⁇ 10 ⁇ 3 cm 3 / m 2 ⁇ 24 h ⁇ atm or less and a water vapor permeability of 1 ⁇ 10 ⁇ 5 g / m 2 ⁇ 24 h or less.
  • 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, ceramic substrates, and the like.
  • the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element ⁇ 100.
  • a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
  • 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.
  • the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the organic EL element can be thinned.
  • the polymer film is JIS K
  • the oxygen permeability measured by the method according to 7126-1987 is 1 ⁇ 10 ⁇ 3 cm 3 / m 2 ⁇ 24 h ⁇ atm or less
  • the water vapor permeability measured by the method according to JIS K 7129-1992 is preferably 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ 24 h or less.
  • sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesively cured from room temperature to 80 ° C. is preferable.
  • a desiccant may be dispersed in the adhesive.
  • 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.
  • a laminated structure of these inorganic layers and layers made of organic materials it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials.
  • the method of forming these films There are no particular limitations on the method of forming these films. For example, 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.
  • hygroscopic compound examples include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
  • metal oxides for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
  • sulfates for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate.
  • metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.
  • perchloric acids eg perchloric acid Barium, magnesium perchlorate, and the like
  • anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • a protective film or a protective plate may be provided 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.
  • the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
  • the low refractive index layer examples include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally 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 diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. The light extraction efficiency does not increase so much.
  • the refractive index distribution a two-dimensional distribution
  • the light traveling in all directions is diffracted, and the light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any layer or in the medium (in the transparent substrate or 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 device of the present invention is front-facing to a specific direction, for example, the light emitting surface of the device by combining a so-called condensing sheet, for example, by providing a structure on the microlens array on the light extraction side of the support substrate (substrate). By condensing in the direction, the luminance in a specific direction can be increased.
  • a quadrangular pyramid having a side of 30 ⁇ m and an apex angle of 90 degrees is arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably within a range of 10 to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
  • the condensing sheet it is possible to use, for example, an LED backlight of a liquid crystal display device that has been put into practical use.
  • 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 / film may be used in combination with the light collecting sheet.
  • 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.
  • Examples of 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 during film formation, if necessary.
  • patterning only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned.
  • a conventionally known method is used. Can do.
  • the 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 or printing.
  • the method is not limited, but a vapor deposition method, an ink jet 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 a car.
  • the display device or display 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. 2 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. 3 is a schematic diagram of a display device using an active matrix method.
  • the display unit A has 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. 3 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
  • the scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated Not)
  • the pixel 3 When the scanning signal is applied from the scanning line 5, the pixel 3 receives the image data signal from the data line 6 and emits light according to the received image data.
  • a full color display can be achieved by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 4 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 When the scanning signal moves to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, since the capacitor 13 holds the charged potential of the image data signal even if the driving of the switching transistor 11 is turned off, the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues.
  • the driving transistor 12 When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
  • the organic EL element 10 emits light by the switching transistor 11 and the drive transistor 12 that are active elements for the organic EL 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.
  • the present invention not only the active matrix method described above, but also a passive matrix light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned.
  • FIG. 5 is a schematic view of a passive matrix display device.
  • a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
  • the pixel 3 connected to the applied scanning line 5 emits light according to the image data signal.
  • a display device with improved luminous efficiency was obtained by using the organic EL element of the present invention.
  • 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 device 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 drive method when used as a display device for moving image reproduction may be either a passive matrix method or an active matrix method.
  • the ⁇ -conjugated compound used in the present invention can be applied to a lighting device including an organic EL element that emits substantially white light.
  • 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 organic EL device forming method of the present invention may be simply arranged by providing a mask only when forming a light emitting layer, a hole transporting layer, an electron transporting layer, etc. 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.
  • 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. 6 shows a schematic diagram of the lighting device, and the organic EL element of the present invention (organic EL element 101 in the lighting device) 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.
  • a nitrogen atmosphere in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more
  • FIG. 7 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.
  • an illumination device with improved luminous efficiency can be obtained.
  • the organic EL device material of the present invention is an organic electroluminescence device material containing a ⁇ -conjugated compound having a structure represented by the general formula (1), wherein the ⁇ -conjugated compound is in a ground state, at least excited.
  • the angle ⁇ between the plane of the ring structure A bonded to the nitrogen atom and the plane of the ring structure composed of the nitrogen atom, carbon atom, and X is 45 to 90 It is within the range of degrees.
  • the ⁇ -conjugated compound according to the present invention as an organic EL element material is used for a light-emitting thin film. You can also.
  • the light-emitting thin film of the present invention contains a ⁇ -conjugated compound having a structure represented by the general formula (1), and the ⁇ -conjugated compound includes a ground state, a lowest excited singlet state, and a lowest excited triplet state.
  • the angle ⁇ formed by the surface of the ring structure A bonded to the nitrogen atom and the surface of the ring structure composed of the nitrogen atom, carbon atom and X is in the range of 45 to 90 degrees.
  • the light-emitting thin film and 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 conventionally known methods such as a vacuum deposition method and a wet method (also referred to as a wet process) can be used.
  • wet method examples 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 light emitting 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, and mesitylene.
  • Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
  • a dispersion method it can be dispersed by a dispersion method such as ultrasonic wave, high shearing force dispersion or media dispersion.
  • 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 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 spin coat method when adopted for film formation, it is preferable to perform the spin coater within a range of 100 to 1000 rpm and within a range of 10 to 120 seconds in a dry inert gas atmosphere.
  • Example 1 ⁇ Production of Organic EL Element 1-1 >> An ITO (Indium Tin Oxide) film having a thickness of 150 nm was formed as an anode on a glass substrate having a thickness of 50 mm ⁇ 50 mm and a thickness of 0.7 mm. After patterning, a transparent substrate with the ITO transparent electrode was attached. After ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen gas, and UV ozone cleaning for 5 minutes, this transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus.
  • ITO Indium Tin Oxide
  • Each of the deposition crucibles in the vacuum deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • the deposition crucible containing HAT-CN was energized and heated, and deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second. A hole injection layer was formed.
  • ⁇ -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.
  • the host compound mCP and the comparative compound 1 as the luminescent compound were co-deposited at a deposition rate of 0.1 nm / second so as to be 92% and 8% by volume, respectively, to form a luminescent layer having a layer thickness of 30 nm.
  • BCP was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a layer thickness of 30 nm.
  • lithium fluoride with a film thickness of 0.5 nm
  • 100 nm of aluminum was vapor-deposited to form a cathode.
  • the non-light emitting surface side of the above element is covered with a can-like glass case shown in FIGS. 6 and 7 in an atmosphere of high purity nitrogen gas having a purity of 99.999% or more, and an electrode lead-out wiring is installed to form an organic EL element. 1-1 was produced.
  • the absolute value ( ⁇ Est) of the difference between the lowest excited singlet energy level and the lowest excited triplet energy level was calculated using molecular orbital calculation software Gaussian 09 (Revision C.01, MJ Frisch, et al, Gaussian, Inc.). , 2010.) using the optimized structure calculated by the density functional method using the functional B3LYP and the basis function 6-31G (d), the time-dependent density functional using the same functional and basis functions as described above.
  • the excitation state was calculated by a functional method (Time-Dependent DFT).
  • the structure of the ground state was obtained by the calculation.
  • the structures of the lowest excited singlet state and the lowest excited triplet state were obtained by calculation using a time-dependent density functional method (Time-Dependent DFT) using the functional B3LYP and the basis function 6-31G (d).
  • the angle ⁇ was calculated using these optimized structures.
  • the angle ⁇ is “a carbon atom adjacent to the condensed ring structure B or C bonded to the nitrogen atom described in the general formula (1)”, “a nitrogen atom described in the general formula (1)”, and “general A plane consisting of three atoms, “atom in ring structure A in which the nitrogen atom described in formula (1) is bonded to ring structure A”, “a nitrogen atom described in general formula (1)” and “general In the ring structure A in which the nitrogen atom described in formula (1) and the ring structure A are bonded to each other and in the ring structure A in which the nitrogen atom described in general formula (1) is bonded to the ring structure A.
  • the atoms were selected so that the angle formed by the two planes of the plane consisting of the three atoms in the range of 0 to 90 degrees was in the range of 0 to 90 degrees.
  • ⁇ conjugate in which ⁇ G , ⁇ S and ⁇ T are 45 degrees or more, and the absolute value of ⁇ S ⁇ G and the absolute value of ⁇ S ⁇ T are smaller than those of the comparative organic EL element 1-1. It can be seen that the organic EL devices 1-2 to 1-15 of the present invention using a compound of the present invention have improved luminous efficiency. It can also be seen that the organic EL devices 1-3 to 1-15 using a ⁇ -conjugated compound having ⁇ Est of 0.5 eV or less have further improved luminous efficiency.
  • polystyrene sulfonate PEDOT / PSS, Bayer, Baytron P Al 4083
  • PEDOT / PSS polystyrene sulfonate
  • 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 used was made of a resistance heating material made of molybdenum or tungsten.
  • ⁇ -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 and luminescent compound 2 were co-deposited at a deposition rate of 0.1 nm / second so as to be 91% and 9% by volume, respectively, to form a luminescent layer having a layer thickness of 30 nm.
  • TPBi was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a layer thickness of 30 nm.
  • the non-light emitting surface side of the above element is covered with a can-like glass case shown in FIGS. 6 and 7 in an atmosphere of high purity nitrogen gas having a purity of 99.999% or more, and an electrode lead-out wiring is installed to form an organic EL element. 2-1.
  • Organic EL element 2-2 In the production of the organic EL element 2-1, mCP is used as the host compound in the light emitting layer, the light emitting compound 2 is used as the light emitting compound, and the comparative compound 1 is used as the third component (assist dopant).
  • Organic EL element 2-2 was produced in the same manner as in the production of organic EL element 2-1, except that the light emitting layer was formed so that the volume% was 13% and 13%.
  • Luminous efficiency and ⁇ Est were measured in the same manner as in Example 1. The results are shown in Table 2. The obtained result showed a relative value where the organic EL element 2-1 was 100.
  • ⁇ G , ⁇ S , and ⁇ T are 45 degrees or more, and the absolute value of ⁇ S ⁇ G and the absolute value of ⁇ S ⁇ T are larger than those of the comparative organic EL elements 2-1 and 2-2. It can be seen that the organic EL elements 2-3 to 2-16 of the present invention using a ⁇ -conjugated compound having a small value have improved luminous efficiency. It can also be seen that the organic EL elements 2-4 to 2-16 using a ⁇ -conjugated compound having ⁇ Est of 0.5 eV or less have further improved luminous efficiency.
  • Example 3 ⁇ Preparation of organic EL element 3-1 >> 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 is heated by energizing a resistance heating boat containing HAT-CN, 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 was deposited at a deposition rate of 0.1 nm / second to form a 30 nm-thick hole transport layer.
  • a resistance heating boat containing comparative compound 1 as a host compound and tris (2-phenylpyridinato) iridium (III) as a luminescent compound was energized and heated, and the deposition rate was 0.1 nm / second, Co-evaporation was performed on the hole transport layer at 0.010 nm / second to form a light emitting layer having a thickness of 40 nm.
  • 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 to a thickness of 0.5 nm, and then 100 nm of aluminum was vapor-deposited to form a cathode to produce an organic EL element 3-1.
  • Example 2 In the same manner as in Example 1, the light emission luminance of the organic EL element 3-1 was measured, and the light emission efficiency was calculated. The relative luminous efficiency of each organic EL element relative to the luminous efficiency of the organic EL element 3-1 was determined. Table 3 shows the measurement results obtained.
  • ⁇ G , ⁇ S , and ⁇ T are 45 degrees or more, and the absolute value of ⁇ S ⁇ G and the absolute value of ⁇ S ⁇ T are smaller than those of the comparative organic EL element 3-1. It can be seen that the organic EL devices 3-2 to 3-15 of the present invention using a conjugated compound have improved luminous efficiency. It can also be seen that the organic EL elements 3-3 to 3-15 using a ⁇ -conjugated compound having ⁇ Est of 0.5 eV or less have further improved luminous efficiency.
  • the organic EL element of the present invention has improved luminous efficiency and 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 Examples include a light source of a sensor. In particular, it can be effectively used as a backlight of a liquid crystal display device and a light source for illumination.

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Abstract

L'invention aborde le problème de la fourniture d'un nouvel élément EL organique ayant une meilleure efficacité d'émission de lumière. L'invention aborde également le problème de la fourniture d'un matériau d'élément EL organique destiné à être utilisé dans ledit élément EL organique, un film mince émettant de la lumière contenant ledit matériau d'élément EL organique, et un dispositif d'affichage et un dispositif d'éclairage dotés dudit élément EL organique. L'élément EL organique selon la présente invention est un élément EL organique ayant au moins une couche émettrice de lumière entre une anode et une cathode, caractérisé en ce que ladite au moins une couche émettrice de lumière contient un composé π-conjugué ayant une structure représentée par la formule générale (1), le composé π-conjugué étant tel que, dans chacun d'un état de mise à la terre, un état de singulet excité le plus bas et un état de triplet excité le plus bas, un angle θ formé entre le plan d'une structure cyclique A liée à un atome d'azote et le plan d'une structure cyclique comprenant un atome d'azote, des atomes de carbone et X est dans la plage de 45 à 90 degrés.
PCT/JP2015/071483 2014-07-31 2015-07-29 Matériau d'élément électroluminescent organique, élément électroluminescent organique, film mince émettant de la lumière, dispositif d'affichage et dispositif d'éclairage WO2016017684A1 (fr)

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CN109912564A (zh) * 2017-12-13 2019-06-21 江苏三月光电科技有限公司 一种以氰基氮杂苯为核心的化合物及其在oled器件上的应用
CN109912494A (zh) * 2017-12-13 2019-06-21 江苏三月光电科技有限公司 一种以氰基苯为核心的化合物及其在oled器件上的应用
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JP2020510322A (ja) * 2017-01-16 2020-04-02 中国科学院長春應用化学研究所 青色有機エレクトロルミネッセンスデバイスおよびその製造方法
CN111303174A (zh) * 2018-12-11 2020-06-19 北京鼎材科技有限公司 一种有机电致发光材料及其应用
JP2020105341A (ja) * 2018-12-27 2020-07-09 日鉄ケミカル＆マテリアル株式会社 熱活性化遅延蛍光発光材料、及び有機電界発光素子
JP2021500439A (ja) * 2017-10-19 2021-01-07 ザ・ユニヴァーシティ・オブ・ダラムＴｈｅ Ｕｎｉｖｅｒｓｉｔｙ ｏｆ Ｄｕｒｈａｍ 熱活性化遅延蛍光分子、前記分子を含む材料および前記材料を含むデバイス
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US10125310B2 (en) 2015-02-06 2018-11-13 Idemitsu Kosan Co., Ltd. Organic electroluminescence element and electronic device
US10351765B2 (en) 2015-02-06 2019-07-16 Idemitsu Kosan Co., Ltd. Organic electroluminescence element and electronic device
WO2016158540A1 (fr) * 2015-03-27 2016-10-06 出光興産株式会社 Élément électroluminescent organique, dispositif électronique et composé
JPWO2016158540A1 (ja) * 2015-03-27 2018-02-08 出光興産株式会社 有機エレクトロルミネッセンス素子、電子機器、および化合物
US10547009B2 (en) 2015-03-27 2020-01-28 Idemitsu Kosan Co., Ltd. Organic electroluminescent element, electronic device and compound
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WO2017210075A1 (fr) * 2016-06-02 2017-12-07 E. I. Du Pont De Nemours And Company Matériaux électroactifs
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JP2019520347A (ja) * 2016-06-02 2019-07-18 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 電気活性材料
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US11271169B2 (en) 2017-08-24 2022-03-08 Samsung Display Co., Ltd. Nitrogen-containing compound and organic electroluminescence device including the same
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US11725013B2 (en) 2017-10-19 2023-08-15 The University Of Durham Thermally activated delayed fluorescence molecules, materials comprising said molecules, and devices comprising said materials
US11563187B2 (en) 2017-11-15 2023-01-24 Samsung Display Co., Ltd. Nitrogen-containing compound-containing compound and organic electroluminescence device including the same
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CN109912564A (zh) * 2017-12-13 2019-06-21 江苏三月光电科技有限公司 一种以氰基氮杂苯为核心的化合物及其在oled器件上的应用
CN109912565A (zh) * 2017-12-13 2019-06-21 江苏三月光电科技有限公司 一种以氰基氮杂苯为核心的化合物及其在有机电致发光器件中的应用
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JPWO2019171891A1 (ja) * 2018-03-07 2021-05-13 日鉄ケミカル＆マテリアル株式会社 有機電界発光素子
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JP7332577B2 (ja) 2018-03-07 2023-08-23 日鉄ケミカル＆マテリアル株式会社 有機電界発光素子
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US11957043B2 (en) 2020-05-06 2024-04-09 Samsung Display Co., Ltd. Light-emitting device and electronic apparatus comprising same

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