WO2016017514A1 - Élément électroluminescent organique, film mince émetteur de lumière, dispositif d'affichage et dispositif d'éclairage - Google Patents

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

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WO2016017514A1
WO2016017514A1 PCT/JP2015/070917 JP2015070917W WO2016017514A1 WO 2016017514 A1 WO2016017514 A1 WO 2016017514A1 JP 2015070917 W JP2015070917 W JP 2015070917W WO 2016017514 A1 WO2016017514 A1 WO 2016017514A1
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group
carbon atoms
compound
organic
electron
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周穂 谷本
池水　大
鈴木　隆嗣
康生 宮田
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コニカミノルタ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/20—Delayed fluorescence emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

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  • the present invention relates to an organic electroluminescence element, a light-emitting thin film, and a display device and an illumination device including the organic electroluminescence element. More specifically, the present invention relates to an organic electroluminescence element with improved luminous efficiency.
  • organic electroluminescence element (hereinafter, also referred to as “organic EL element” or “organic electroluminescence element”) using organic electroluminescence (Electro Luminescence: hereinafter abbreviated as “EL”) emits planar light.
  • EL Organic electroluminescence
  • This technology has already been put into practical use as a new light-emitting system that enables this.
  • Organic EL elements are applied not only to electronic displays but also recently as lighting devices, and their development is expected.
  • TTA triplet-triplet annihilation
  • TTF triplet-triplet fusion
  • thermally activated delayed fluorescence (reverse intersystem crossing: hereinafter, abbreviated as “RISC” where appropriate) is a phenomenon that uses a characteristic that causes triplet excitons to singlet excitons.
  • RISC reverse intersystem crossing
  • TADF Thermally Activated Delayed Fluorescence
  • a light emitting layer composed of a host compound and a light emitting compound contains a compound exhibiting TADF properties as a third component (hereinafter also referred to as an assist dopant) in the light emitting layer, it is effective for high luminous efficiency.
  • an assist dopant a compound exhibiting TADF properties as a third component
  • It is known see, for example, Non-Patent Document 3.
  • the triplet excitons generate singlet excitons with reverse intersystem crossing (RISC). be able to.
  • RISC reverse intersystem crossing
  • the TADF mechanism is a compound in which the difference ( ⁇ Est) between the singlet excitation energy level and the triplet excitation energy level ( ⁇ Est (TADF in FIG. 1A) is smaller than that of an ordinary fluorescent compound material. ) Is smaller than ⁇ Est (F).) Is a light emission mechanism that utilizes the phenomenon that reverse intersystem crossing from triplet excitons to singlet excitons occurs.
  • the present inventor has an organic layer group including at least one light emitting layer between the anode and the cathode, and at least one layer of the organic layer group.
  • an organic electroluminescence device containing a ⁇ -conjugated compound which is an aromatic hydrocarbon compound having an electron-donating group and an electron-withdrawing group in the same molecule represented by the general formula (1). It was found that an organic electroluminescence element that can be driven at a high speed and that can obtain high luminous efficiency can be realized.
  • An organic electroluminescence device having an organic layer group including at least one light emitting layer between an anode and a cathode, At least one layer of the organic layer group contains a ⁇ -conjugated compound having a structure represented by the following general formula (1).
  • A represents an electron-withdrawing group
  • D represents an electron-donating group.
  • m and n are each independently an integer of 1 or 2.
  • X represents an aromatic hydrocarbon group selected from structures represented by the following general formulas (1a) to (1k).
  • R 1 , R 2 , Ra, Rb, Rc and Rd each independently represents a hydrogen atom or a substituent.
  • p, q, r and s each independently represent an integer of 0 to 4. These substituents may be the same or different, and each substituent may be bonded to form a ring.
  • the attractive group represents an aromatic heterocyclic group, a sulfonyl group (—SO 2 R 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • a sulfenyl group (—SOR 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms), a cyano group (—CN), halogeno A group, a carbonyl group (—COR 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms), a pentafluorophenyl group (—C 6 F 5) a trifluoromethyl group (-CF 3), trifluoromethyl Eniru group (-C 6 H 4 CF 3) , and boryl group (-BR 1 2; R 1 represents an aromatic heterocyclic group of aromatic hydrocarbon group having 6 to 30 carbon atoms, or 3 to 20 carbon atoms
  • R 1 , R 2 , Ra, Rb, Rc and Rd in the aromatic hydrocarbon group having the structure represented by the general formulas (1a) to (1k) is an electron donating group
  • the donating group is an aromatic heterocyclic group having 3 to 20 carbon atoms, an amino group (—NH 2 ), an arylamino group (—NHR 1 or —NR 1 2 ;
  • R 1 is an aromatic carbon group having 6 to 30 carbon atoms;
  • R 1 is a linear or cyclic hydrocarbon group having 1 to 10 carbon atoms), and an aryloxy group ( —OR 2 ;
  • R 2 represents a linear or cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • R 1 , R 2 , Ra, Rb, Rc and Rd in the aromatic hydrocarbon group having the structure represented by the general formulas (1a) to (1k) is an electron-withdrawing group
  • the attractive group represents an aromatic heterocyclic group, a sulfonyl group (—SO 2 R 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • a sulfenyl group (—SOR 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms), a cyano group (—CN), halogeno A group, a carbonyl group (—COR 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms), a pentafluorophenyl group (—C 6 F 5) a trifluoromethyl group (-CF 3), trifluoromethyl Eniru group (-C 6 H 4 CF 3) , and boryl group (-BR 1 2; R 1 represents an aromatic heterocyclic group of aromatic hydrocarbon group having 6 to 30 carbon atoms, or 3 to 20 carbon atoms And at least one of R 1 , R 2 , Ra, Rb, Rc and Rd in the general formulas (1a) to (1k) is an electron donating group.
  • the electron donating group is an aromatic heterocyclic group having 3 to 20 carbon atoms, an amino group (—NH 2 ), an arylamino group (—NHR 1 or —NR 1 2 ; R 1 has 6 to 30 carbon atoms)
  • X in the ⁇ -conjugated compound having the structure represented by the general formula (1) is the general formula (1a), (1b), (1d), (1e), (1g), (1h), (1i
  • X in the ⁇ -conjugated compound having the structure represented by the general formula (1) is the general formula (1a), (1b), (1d), (1e), (1g), (1h), (1i ) Or (1j), wherein at least one of R 1 , R 2 , Ra, Rb, Rc and Rd is an electron-withdrawing group, and at least one is an electron donor 6.
  • the group according to item 5, wherein all of R 1 , R 2 , Ra, Rb, Rc and Rd which are non-corresponding to the electron-withdrawing group and the electron-donating group are hydrogen atoms.
  • the absolute value ( ⁇ Est) of the energy difference between the lowest excited singlet level and the lowest excited triplet level of the ⁇ -conjugated compound having the structure represented by the general formula (1) is 0.5 eV or less.
  • 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.
  • the organic electroluminescent element according to any one of items 1 to 7.
  • a luminescent thin film comprising a ⁇ -conjugated compound having a structure represented by the following general formula (1).
  • A represents an electron-withdrawing group
  • D represents an electron-donating group.
  • m and n are each independently an integer of 1 or 2.
  • X represents an aromatic hydrocarbon group selected from structures represented by the following general formulas (1a) to (1k).
  • R 1 , R 2 , Ra, Rb, Rc and Rd each independently represents a hydrogen atom or a substituent.
  • p, q, r and s each independently represent an integer of 0 to 4. These substituents may be the same or different, and each substituent may be bonded to form a ring.
  • 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.
  • a display device comprising the organic electroluminescence element according to any one of items 1 to 9.
  • An organic electroluminescence device according to any one of items 1 to 9 is provided.
  • the above-described means of the present invention can provide an organic electroluminescence device that achieves high luminous efficiency with a reduced driving voltage.
  • a light-emitting thin film containing the conjugated compound according to the present invention, and a display device and a lighting device including the organic electroluminescence element can be provided.
  • the voltage required for light emission varies greatly depending on the physical properties of the charge transfer thin film existing between the electrodes and the configuration of these materials. Since the organic electroluminescence element that can be driven at a low voltage has a small load when energized, it can be expected that the power consumption can be kept low and the life of the element can be improved. In addition, an improvement in luminous efficiency with respect to electric power is expected.
  • the material for an organic thin film used for an organic EL element As a material for an organic thin film used for an organic EL element, a material having a characteristic capable of transporting carriers such as electrons and holes is required.
  • the material used for the light-emitting layer is required to have a property of efficiently transporting both electrons and holes because the charges are recombined. Therefore, the compound preferably has bipolar properties.
  • the compound having an electron donating group and an electron withdrawing group in the same molecule is bipolar, which is advantageous for charge transfer in the thin film, which is preferable from the viewpoint of lowering the driving voltage.
  • bipolar compounds tend to separate HOMO and LUMO, and the electronic transition between HOMO and LUMO necessary for light emission tends to be forbidden, resulting in low oscillator strength and light emission. There is a tendency to become difficult.
  • an aromatic hydrocarbon compound is suitable as a field for generating HOMO-LUMO overlap, and is incorporated into a compound having an electron-donating group and an electron-withdrawing group, so that high luminous efficiency and high charge transport are achieved. It is possible to achieve both performance.
  • the aromatic hydrocarbon compound having an electron donating group and an electron withdrawing group preferably has a size of a ⁇ -conjugated surface of about 4 rings.
  • Schematic diagram showing energy diagrams of normal fluorescent compounds and TADF compounds Schematic showing energy diagram in the presence of assist dopant
  • Schematic diagram showing an example of a display device composed of organic EL elements Schematic diagram showing an example of the structure of a display device using an active matrix method
  • Schematic showing the pixel circuit Schematic diagram showing an example of the structure of a display device using a passive matrix method
  • the organic electroluminescence device of the present invention is an organic electroluminescence device having an organic layer group including at least one light emitting layer between an anode and a cathode, wherein at least one layer of the organic layer group is represented by the general formula (1). And a ⁇ -conjugated compound having a structure having an electron-donating group and an electron-withdrawing group in the same molecule.
  • At least one of R 1 , R 2 , Ra, Rb, Rc and Rd in the aromatic hydrocarbon group having a structure represented by the general formulas (1a) to (1k) is preferable.
  • the electron-withdrawing group is an aromatic heterocyclic group, a sulfonyl group (—SO 2 R 1 ; R 1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms, or 3 carbon atoms.
  • a cyano group (—CN), a halogeno group, a carbonyl group (—COR 1 ;
  • R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • Pentafluorophenyl group (—C 6 F 5 ), trifluoro A romethyl group (—CF 3 ), a trifluoromethylphenyl group (—C 6 H 4 CF 3 ), and a boryl group (—BR 1 2 ; R 1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a carbon number; 3 to 20 aromatic heterocyclic groups)
  • the localization of LUMO on the electron-withdrawing group is promoted, and the bipolar property of the whole compound is improved.
  • the drive voltage can be further lowered and higher luminous efficiency can be obtained.
  • R 1 , R 2 , Ra, Rb, Rc and Rd in the aromatic hydrocarbon group having the structure represented by the general formulas (1a) to (1k) is an electron donating group
  • the electron-donating group is an aromatic heterocyclic group having 3 to 20 carbon atoms, an amino group (—NH 2 ), an arylamino group (—NHR 1 or —NR 1 2 ; R 1 is an aromatic group having 6 to 30 carbon atoms.
  • X in the ⁇ -conjugated compound having the structure represented by the general formula (1) is the general formula (1a), (1b), (1d), (1e), (1g), (1h), Since the aromatic hydrocarbon group represented by (1i) or (1j) has a small number of condensed rings or a zigzag conjugated structure, it has a structure in which a large number of rings are condensed in series. This is advantageous in that the excitation energy level is higher than that of the compound having the same.
  • X in the ⁇ -conjugated compound having the structure represented by the general formula (1) is represented by the general formula (1a), ( It is an aromatic hydrocarbon group represented by 1b), (1d), (1e), (1g), (1h), (1i) or (1j) from the viewpoint of obtaining high luminous efficiency. preferable.
  • the absolute value ( ⁇ Est) of the energy difference between the lowest excited singlet level and the lowest excited triplet level of the ⁇ -conjugated compound having the structure represented by the general formula (1) is 0.5 eV or less.
  • ⁇ Est thermally activated delayed fluorescence
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • Organic EL light emission methods a) “phosphorescence emission” that emits light when returning from the triplet excited state to the ground state, and b) “fluorescence emission that emits light when returning from the singlet excited state to the ground state. There are two ways.
  • a rare metal such as iridium, palladium, or platinum, which is a rare metal.
  • a white metal such as iridium, palladium, or platinum, which is a rare metal.
  • the price of the metal itself is a big problem for the industry.
  • 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 Excited triplet-triplet annihilation
  • a light emission method using delayed fluorescence has been introduced.
  • the TTA method that originates from collisions between triplet excitons can be described by the following formula (I). That is, there is a merit that a part of triplet excitons, in which the energy of excitons has been converted only to heat due to non-radiation deactivation, can cross back to singlet excitons that can contribute to light emission. Even in an actual organic EL device, it is possible to obtain an external extraction quantum efficiency approximately twice that of a conventional fluorescent light emitting device.
  • T * represents a triplet exciton
  • S * represents a singlet exciton
  • S represents a ground state molecule
  • Thermal activated delayed fluorescence (TADF) compound is a method that can solve the above-mentioned problems of TTA.
  • Fluorescent compounds have the advantage of being able to design an infinite number of molecules as described above. That is, among the molecularly designed compounds, there is a compound in which the absolute value ( ⁇ Est) of the energy level difference between the triplet excited state and the singlet excited state is extremely close (see FIG. 1A).
  • 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.
  • Non-Patent Documents 1 to 3 described above by introducing an electron-withdrawing skeleton such as a cyano group, a sulfonyl group, or a triazine and an electron-donating skeleton such as a carbazole or a diphenylamino group, LUMO and HOMO is localized.
  • an electron-withdrawing skeleton such as a cyano group, a sulfonyl group, or a triazine
  • an electron-donating skeleton such as a carbazole or a diphenylamino group
  • Rigidity described here means that there are few sites that can move freely in the molecule, for example, by suppressing free rotation in the bond between rings in the molecule and introducing a condensed ring with a large ⁇ conjugate plane. To do.
  • TADF compounds have various problems in terms of their light emission mechanism and molecular structure.
  • the electronic state of the molecule is a donor / acceptor type molecule in which the HOMO site and the LUMO site are separated. It becomes a state close to the inner CT (intramolecular charge transfer state).
  • Such a stabilization state is not limited to the formation between two molecules, but can also be formed between a plurality of molecules such as between three molecules, between five molecules, etc.
  • various stabilization states having a wide distribution Therefore, the shape of the absorption spectrum and emission spectrum is 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 the following two major problems.
  • fluorescence zero-zero band the rising wavelength on the short wavelength side of the emission spectrum (hereinafter referred to as “fluorescence zero-zero band”) is shortened, that is, the S 1 is increased (the lowest excitation singlet energy is increased). It is to do.
  • the fluorescence zero-zero band is shortened, the phosphorescence zero-zero band derived from T 1 having lower energy than S 1 is also shortened (higher T 1 ). Therefore, the compound used in the host compound in order not to cause reverse energy transfer from the dopant, arises the need to 1 reduction and high T 1 of high S.
  • 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.
  • a transition that is deactivated from a triplet excited state to a ground state is a forbidden transition, and therefore the existence time (exciton lifetime) in the triplet excited state is from several hundred microseconds to millisecond. It is very long with second order. Therefore, even if the T 1 energy of the host compound is higher than that of the fluorescent compound, the reverse energy from the triplet excited state of the fluorescent compound to the host compound is determined from the length of the existence time. The probability of causing movement increases.
  • the present invention includes a ⁇ -conjugated compound (including a fluorescent compound) that suppresses the structural change of the excited state as described above and a ⁇ -conjugated compound having a short triplet excited state as design philosophy. .
  • 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
  • Gaussian 09 (Revision C.01, MJ Frisch, et al, Gaussian, Inc., 2010.) manufactured by Gaussian, USA was used as molecular orbital calculation software.
  • HOMO and LUMO are substantially separated means that the HOMO orbital distribution calculated by the above molecular calculation and the central part of the LUMO orbital distribution are separated, more preferably the HOMO orbital distribution and the LUMO orbital. This means that the distributions of do not overlap.
  • ⁇ Est E (S 1 ) ⁇ E (T 1 ) It is.
  • ⁇ Est calculated using the same calculation method as described above is preferably 0.5 eV or less, more preferably 0.2 eV or less, and further preferably 0.1 eV or less.
  • the lowest excited singlet energy 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.
  • a solvent that does not affect the aggregation state of the fluorescent compound that is, a solvent having a small influence of the solvent effect, for example, a nonpolar solvent such as cyclohexane or toluene can be used.
  • the lowest excited triplet energy (T 1 ) of the ⁇ -conjugated compound used in the present invention was calculated from the photoluminescence (PL) characteristics of the solution or thin film. For example, as a calculation method in a thin film, after making a dispersion of a dilute ⁇ -conjugated compound into a thin film, using a streak camera, the transient PL characteristics are measured to separate the fluorescent component and the phosphorescent component, The lowest excited triplet energy can be obtained from the lowest excited singlet energy with the energy difference as ⁇ Est.
  • the light emitting layer used in the present invention is composed of a single layer or a plurality of layers, and when there are a plurality of light emitting layers, a non-light emitting intermediate layer may be provided between the light emitting layers.
  • a hole blocking layer also referred to as a hole blocking layer
  • an electron injection layer also referred to as a cathode buffer layer
  • An electron blocking layer also referred to as an electron barrier layer
  • a hole injection layer also referred to as an anode buffer layer
  • the electron transport layer used in the present invention is a layer having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. Moreover, you may be comprised by multiple layers.
  • the hole transport layer used in the present invention is a layer having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. Moreover, you may be comprised by multiple layers.
  • the constituent layers excluding the anode and the cathode are also referred to as “organic layer group”.
  • the organic EL element of the present invention may be a so-called tandem element in which a plurality of light emitting units including at least one light emitting layer are stacked.
  • first light emitting unit is all the same, May be different.
  • Two light emitting units may be the same, and the remaining one may be different.
  • the plurality of light emitting units constituting the tandem structure may be directly stacked or may be stacked via the intermediate layer as described above.
  • the intermediate layer is generally called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer. It has electrons in the adjacent layer on the anode side and holes in the adjacent layer on the cathode side. Any layer having a function of supplying can be formed using a known material.
  • Examples of materials used for forming the intermediate layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO 2 , TiN, ZrN, HfN, TiOx, VOx, CuI, InN, GaN, Conductive inorganic compound layers such as CuAlO 2 , CuGaO 2 , SrCu 2 O 2 , LaB 6 , RuO 2 and Al, two-layer films such as Au / Bi 2 O 3 , SnO 2 / Ag / SnO 2 , ZnO / Multi-layer film such as Ag / ZnO, Bi 2 O 3 / Au / Bi 2 O 3 , TiO 2 / TiN / TiO 2 , TiO 2 / ZrN / TiO 2 , fullerenes such as C 60 , conductivity such as oligothiophene Examples include organic layers, conductive organic compound layers such as metal phthalocyanines, metal-free phthalocyanines, metal porphyrins
  • Preferred examples of the configuration within the light emitting unit include, for example, the configurations of (1) to (7) exemplified as the typical element configurations described above except that the anode and the cathode are excluded. It is not limited.
  • 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. Specification, U.S. Pat. No. 6,337,492, International Publication No.
  • 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 homogeneity 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. In view of the above, it is preferable to adjust within the range of 2 nm to 5 ⁇ m, more preferably within the range of 2 to 500 nm, and even more preferably within the range of 5 to 200 nm.
  • each light emitting layer used in the present invention is preferably adjusted in the range of 2 nm to 1 ⁇ m, more preferably adjusted in the range of 2 to 200 nm, and further preferably 3 to 150 nm. Adjusted within range.
  • the light-emitting layer used in the present invention contains a light-emitting dopant (a light-emitting compound, a light-emitting dopant compound, a dopant compound, also simply referred to as a dopant), and further, the above-described host compound (matrix material, light-emitting host compound, simply host). It is also preferable to contain.
  • a light-emitting dopant a light-emitting compound, a light-emitting dopant compound, a dopant compound, also simply referred to as a dopant
  • the above-described host compound matrix material, light-emitting host compound, simply host. It is also preferable to contain.
  • Luminescent dopant As the luminescent dopant, a fluorescent luminescent dopant (also referred to as a fluorescent luminescent compound, a fluorescent dopant, or a fluorescent compound) and a phosphorescent dopant (phosphorescent compound, phosphorescent dopant, phosphorescence). It is also referred to as a functional compound).
  • a fluorescent luminescent dopant also referred to as a fluorescent luminescent compound, a fluorescent dopant, or a fluorescent compound
  • phosphorescent dopant phosphorescent compound, phosphorescent dopant, phosphorescence
  • It also referred to as a functional compound.
  • at least one light emitting layer contains a fluorescent compound described later and a ⁇ -conjugated compound functioning as a light emission auxiliary agent (assist dopant).
  • the light emitting layer preferably contains a fluorescent compound within the range of 5 to 40% by mass, particularly within the range of 10 to 30% by mass.
  • the concentration of the fluorescent compound in the light emitting layer can be arbitrarily determined based on the fluorescent compound having a specific structure to be used and the requirements of the device, and is uniform in the thickness direction of the light emitting layer. It may be contained in a concentration, or may have a concentration distribution in an arbitrary pattern.
  • luminescent dopants using delayed fluorescence have been developed, and these may be used.
  • Specific examples of the luminescent dopant using delayed fluorescence include, for example, compounds described in International Publication No. 2011/156793, Japanese Patent Application Laid-Open No. 2011-213643, Japanese Patent Application Laid-Open No. 2010-93181, and the like. Is not limited to these.
  • the fluorescent compounds used in the present invention may be used in combination of two or more types, and combinations of fluorescent compounds having different structures or combinations of fluorescent compounds and phosphorescent compounds. Also good. Thereby, arbitrary luminescent colors can be obtained.
  • the ⁇ -conjugated compound according to the present invention can be used for assisting light emission of different fluorescent compounds or phosphorescent compounds.
  • the light emitting layer contains a host having a mass ratio of 100% or more with respect to the ⁇ -conjugated compound according to the present invention, and 0.1 to 0.1 mass ratio with respect to the ⁇ -conjugated compound according to the present invention. It is preferable that different fluorescent substances or phosphorescent compounds exist within a range of 50%.
  • the substance contained in the light-emitting layer includes three or more components including the host compound. It is preferable.
  • a ⁇ -conjugated compound preferably a ⁇ -conjugated compound having an absolute value ( ⁇ Est) of a difference between the lowest excited singlet energy level and the lowest excited triplet energy level of 0.5 eV or less. It is also suitable from a viewpoint of high luminous efficiency expression to contain a system compound and at least 1 sort (s) of a fluorescent compound and a phosphorescent compound. More preferably, the light emitting layer further contains a host compound.
  • the number of each component contained in the light-emitting layer of the ⁇ -conjugated compound, the luminescent compound, and the host compound is not limited, but it is more preferable that at least one of the three components is contained.
  • the light emitting layer has a difference in absolute value between the lowest excited singlet energy level and the lowest excited triplet energy level ( ⁇ Est) of 0.5 eV or less, the ⁇ -conjugated compound according to the present invention, a luminescent compound,
  • the ⁇ -conjugated compound according to the present invention acts as an assist dopant.
  • the light emitting layer contains the ⁇ -conjugated compound and the luminescent compound according to the present invention and does not contain the host compound, 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.
  • light emitting layer the energy level of the S 1 and T 1 of the case containing the two components of the light emitting compound and [pi conjugated compound according to the present invention, [pi-conjugated compounds, S 1 luminescent compound higher than the energy level of T 1 and is preferable.
  • FIG. 1B and FIG. 1C are schematic views when the ⁇ -conjugated compound of the present invention acts as an assist dopant and a host compound, respectively.
  • 1B and 1C are examples, and the generation process of the triplet exciton generated on the ⁇ -conjugated compound according to the present invention is not limited to the electric field excitation, and energy from the light emitting layer or the peripheral layer interface. Movement, electronic movement, etc. are also included.
  • a fluorescent compound is used as a light-emitting material, but the present invention is not limited thereto, and a phosphorescent compound may be used, or a fluorescent compound and a phosphorescent compound are used. Both of these may be used.
  • the light-emitting layer contains 100% or more of the host compound by mass ratio with respect to the ⁇ -conjugated compound, and the fluorescent compound or phosphorescent compound is It is preferably contained within a range of 0.1 to 50% by mass ratio with respect to the ⁇ -conjugated compound.
  • the light-emitting layer has a mass ratio of 0.1 to 50% with respect to the ⁇ -conjugated compound. It is preferable to contain within.
  • 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.
  • the light emitting layer of one layer or plural layers contains a plurality of light emitting dopants having different light emission colors and exhibits white light emission.
  • At least one layer of the organic layer group contains a ⁇ -conjugated compound having a structure represented by the following general formula (1).
  • 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 is preferably 0.5 eV or less.
  • the ⁇ -conjugated compound having the structure represented by the general formula (1) according to the present invention converts a triplet exciton generated on the ⁇ -conjugated compound into a singlet exciton by reverse intersystem crossing (RISC).
  • RISC reverse intersystem crossing
  • it is a compound that has the function of increasing the luminous efficiency as an assist dopant for improving the luminous efficiency by not deactivating, and the function of improving the luminous efficiency as a fluorescent compound having a TADF property. Useful as a material.
  • the luminous efficiency can be improved by including a ⁇ -conjugated compound as an assist dopant or a host compound together with a light-emitting compound in the light-emitting layer of the organic EL element.
  • A represents an electron withdrawing group
  • D represents an electron donating group
  • m and n are each independently an integer of 1 or 2.
  • X represents an aromatic hydrocarbon group selected from structures represented by the following general formulas (1a) to (1k).
  • R 1 , R 2 , Ra, Rb, Rc and Rd each independently represent a hydrogen atom or a substituent.
  • p, q, r and s each independently represent an integer of 0 to 4. These substituents may be the same or different, and each substituent may be bonded to form a ring.
  • R 1 , R 2 , Ra, Rb, Rc and Rd in the aromatic hydrocarbon group having the structure represented by the general formulas (1a) to (1k) is an electron withdrawing group
  • the electron-withdrawing group is an aromatic heterocyclic group, a sulfonyl group (—SO 2 R 1 ;
  • R 1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • a sulfenyl group (—SOR 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms or an aromatic heterocyclic group having 3 to 20 carbon atoms), a cyano group (—CN)
  • a halogeno group, a carbonyl group (—COR 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms), a pentafluorophenyl group (—C 6 F 5), trifluoromethyl group (-CF 3), trifluoroacetic Butylphenyl group (-C 6 H 4 CF 3)
  • boryl group (-BR 1 2; R 1 represents an aromatic heterocyclic group of aromatic hydrocarbon group having 6 to 30 carbon atoms, or 3 to 20 carbon atoms It is a preferred embodiment that it is at least one kind selected from.
  • R 1 , R 2 , Ra, Rb, Rc and Rd in the aromatic hydrocarbon group having the structure represented by the general formulas (1a) to (1k) is an electron donating group
  • the electron-donating group is an aromatic heterocyclic group having 3 to 20 carbon atoms, an amino group (—NH 2 ), an arylamino group (—NHR 1 or —NR 1 2 ; R 1 is an aromatic group having 6 to 30 carbon atoms.
  • R 1 is a linear or cyclic hydrocarbon group having 1 to 10 carbon atoms
  • aryloxy At least selected from a group (—OR 2 ; R 2 represents a linear or cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms).
  • R 2 represents a linear or cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • One type is a
  • R 1 , R 2 , Ra, Rb, Rc and Rd in the aromatic hydrocarbon group having the structure represented by the general formulas (1a) to (1k) is an electron-withdrawing group
  • the electron-withdrawing group is an aromatic heterocyclic group, a sulfonyl group (—SO 2 R 1 ; R 1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • a sulfenyl group (—SOR 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms), a cyano group (—CN ), A halogeno group, a carbonyl group (—COR 1 ; R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms), a pentafluorophenyl group (— C 6 F 5), trifluoromethyl group (-CF 3), trifluoperazine Methylphenyl group (-C 6 H 4 CF 3) , and boryl group (-BR 1 2; R 1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms It is at least one kind selected from.
  • R 1 , R 2 , Ra, Rb, Rc and Rd in the general formulas (1a) to (1k) is an electron donating group
  • the electron donating group has 3 to 3 carbon atoms.
  • R 1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms, or 3 to 20 carbon atoms Represents an aromatic heterocyclic group), an alkoxy group (—OR 1 ;
  • R 1 is a straight or cyclic hydrocarbon group having 1 to 10 carbon atoms), and an aryloxy group (—OR 2 ;
  • R 2 is a straight chain
  • a cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms is there.
  • X in the ⁇ -conjugated compound having the structure represented by the general formula (1) is the general formula (1a), (1b), (1d), (1e), (1g), (1h), A preferred embodiment is an aromatic hydrocarbon group represented by (1i) or (1j).
  • X in the ⁇ -conjugated compound having the structure represented by the general formula (1) is the general formula (1a), (1b), (1d), (1e), (1g), (1h) , (1i) or (1j), wherein at least one of R 1 , R 2 , Ra, Rb, Rc and Rd is an electron-withdrawing group, and at least 1 One is an electron donating group, and it is a preferred embodiment that all of R 1 , R 2 , Ra, Rb, Rc and Rd not corresponding to the electron withdrawing group and the electron donating group are hydrogen atoms.
  • R 1 , R 2 , R a , R b , R c , and R d represent a substituent
  • substituents include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.
  • a cycloalkyl group eg, cyclopentyl group, cyclohexyl group, etc.
  • an alkenyl group eg, vinyl group, allyl group, etc.
  • an alkynyl group eg, ethynyl group, propargyl group, etc.
  • an aromatic hydrocarbon group aromatic Also referred to as hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xyl group Group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group
  • Cycloalkylthio group eg, cyclopentylthio group, cyclohexylthio group, etc.
  • arylthio group eg, phenylthio group, naphthylthio group, etc.
  • alkoxycarbonyl group eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group
  • Octyloxycarbonyl group dodecyloxycarbonyl group, etc.
  • aryloxycarbonyl group eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.
  • sulfamoyl group eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group
  • indole ring indazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, isoindole ring, naphthyridine ring, phthalazine ring, carbazole ring, carboline ring, diaza
  • carbazole ring in which one of carbon atoms constituting carboline ring is replaced by nitrogen atom
  • acridine ring in which one of carbon atoms constituting carboline ring is replaced by nitrogen atom
  • acridine ring in which one of carbon atoms constituting carboline ring is replaced by nitrogen atom
  • acridine ring in which one of carbon atoms constituting carboline ring is replaced by nitrogen atom
  • acridine ring in which one of carbon atoms constituting carboline ring is replaced by nitrogen atom
  • substituents may be further substituted with the above substituents. Further, these substituents may be bonded together to form a ring.
  • the absolute value ( ⁇ Est) of the energy difference between the lowest excited singlet level and the lowest excited triplet level of the ⁇ -conjugated compound having the structure represented by the general formula (1) according to the present invention is , 0.5 eV or less is preferable.
  • 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 the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant used in the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. Just do it.
  • the phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL element. Specific examples of known phosphorescent dopants that can be used in the present invention include compounds described in the following documents.
  • preferable phosphorescent dopants include organometallic complexes having Ir as a central metal. More preferably, a complex containing at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, and metal-sulfur bond is preferable.
  • the fluorescent compound that can be used in combination with the ⁇ -conjugated compound according to the present invention is not particularly limited.
  • a fluorescent compound having a ⁇ Est of greater than 0.5 eV can be suitably used.
  • the light emitting layer preferably contains a ⁇ -conjugated compound according to the present invention, at least one of a fluorescent compound and a phosphorescent compound, and a host compound.
  • the host compound used in the present invention is a compound mainly responsible for charge injection and transport in the light emitting layer, and its own light emission is not substantially observed in the organic EL device.
  • the host compound preferably has a mass ratio in the layer of 20% or more among the compounds contained in the light emitting layer.
  • 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 host compound used with the fluorescent compound used in the present invention is not particularly limited, but has an excitation energy larger than the excitation singlet energy of the fluorescent compound according to the present invention from the viewpoint of reverse energy transfer. Further preferred are those having an excitation triplet energy greater than the excitation triplet energy of the fluorescent compound according to the present invention.
  • US Patent Application Publication No. 2005/0112407 US Patent Application Publication No. 2009/0017330, US Patent Application Publication No. 2009/0030202, US Patent Application Publication No. 2005/0238919 , International Publication No. 2001/039234, International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No.
  • the host compound is responsible for carrier transport and exciton generation in the light emitting layer. Therefore, it can exist stably in all active species states such as cation radical state, anion radical state, and excited state, and does not cause chemical changes such as decomposition and addition reaction. It is preferable not to move at the angstrom level.
  • the light-emitting dopant used in combination exhibits TADF light emission
  • the T 1 energy of the host compound itself is high, and the host compounds are associated with each other.
  • the host compound is a molecular structure such as not to lower T 1 of Appropriate design is required.
  • the host compound itself must have high electron hopping mobility, high hole hopping movement, and small structural change when it is in a triplet excited state. It is.
  • Representative examples of host compounds satisfying such requirements include a carbazole skeleton, an azacarbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, or an azadibenzofuran skeleton, which have high T 1 energy and an extended ⁇ conjugate of a 14 ⁇ electron system. Those having a skeleton as a partial structure are preferred.
  • the light-emitting layer contains a carbazole derivative
  • aryl includes not only an aromatic hydrocarbon ring but also an aromatic heterocyclic ring.
  • the carbazole derivative having at least one is preferred.
  • the carbazole derivative is preferably a compound having two or more conjugated structures having 14 ⁇ electrons or more in order to further enhance the effects of the present invention.
  • the compound represented by the following general formula (I) is also preferable. This is because the compound represented by the following general formula (I) has a condensed ring structure, and therefore a ⁇ electron cloud spreads, the carrier transportability is high, and the glass transition temperature (Tg) is high. Further, generally, the condensed aromatic ring tends to have a small triplet energy (T 1 ), but the compound represented by the general formula (I) has a high T 1 and has a short emission wavelength (that is, T 1). and larger S 1) it can be suitably used also for the light emitting material.
  • X 101 represents NR 101 , an oxygen atom, a sulfur atom, CR 102 R 103 or SiR 102 R 103 .
  • y 1 to y 8 each represents CR 104 or a nitrogen atom.
  • R 101 to R 104 each represent a hydrogen atom or a substituent, and may be bonded to each other to form a ring.
  • Ar 101 and Ar 102 each represent an aromatic ring and may be the same or different.
  • n101 and n102 represents an each an integer of 0 to 4, when R 101 is a hydrogen atom, n101 represents an integer of 1-4.
  • R 101 to R 104 in the general formula (I) represent hydrogen or a substituent, and the substituent referred to here refers to what may be contained within a range not inhibiting the function of the host compound used in the present invention, for example, In the case where a substituent is introduced in the synthetic scheme, the compound having the effect of the present invention is defined as being included in the present invention.
  • Examples of the substituent represented by each of R 101 to R 104 include linear or branched alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group).
  • alkenyl group eg, vinyl group, allyl group, etc.
  • alkynyl group eg, ethynyl group, propargyl group, etc.
  • aromatic hydrocarbon ring group aromatic Also referred to as carbocyclic group, aryl group, etc.
  • benzene ring biphenyl, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m- Terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, indene ring, fluorene ring A group derived from a fluoranthrene ring, a naphthacene ring, a pentacene ring, a perylene ring, a pentaphen ring, a picene ring, a pyrene ring, a pyrantolen ring, an anthraanthrene ring, tetralin, etc.), an aromatic heterocyclic group (for example, a furan
  • azacarbazole ring non-aromatic hydrocarbon ring group (eg, cyclopentyl group, cyclohexyl group, etc.), non-aromatic heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl) Group), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) Etc.), aryloxy group (for example, phenoxy group, naphthyloxy group) Etc.), alkylthio groups (eg, methylthio group, e
  • substituents may be further substituted with the above substituents.
  • a plurality of these substituents may be bonded to each other to form a ring.
  • y 1 to y 8 in the general formula (I) preferably at least three of y 1 to y 4 or at least three of y 5 to y 8 are represented by CR 102 , more preferably y 1 to y 8 are all CR 102 .
  • Such a skeleton is excellent in hole transport property or electron transport property, and can efficiently recombine and emit holes / electrons injected from the anode / cathode in the light emitting layer.
  • a compound in which X 101 is NR 101 , an oxygen atom, or a sulfur atom in general formula (I) is preferable as a structure having a shallow LUMO energy level and excellent electron transport properties. More preferably, the condensed ring formed with X 101 and y 1 to y 8 is a carbazole ring, an azacarbazole ring, a dibenzofuran ring or an azadibenzofuran ring.
  • R 101 is an aromatic hydrocarbon ring which is a ⁇ -conjugated skeleton among the substituents mentioned above. It is preferably a group or an aromatic heterocyclic group. Further, these R 101 may be further substituted with the substituents represented by R 101 to R 104 described above.
  • examples of the aromatic ring represented by Ar 101 and Ar 102 include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • the aromatic ring may be a single ring or a condensed ring, and may be unsubstituted or may have a substituent similar to the substituents represented by R 101 to R 104 described above.
  • examples of the aromatic hydrocarbon ring represented by Ar 101 and Ar 102 include the aromatic hydrocarbon rings exemplified as the substituents represented by R 101 to R 104 described above. Examples include the same ring as the group.
  • examples of the aromatic heterocycle represented by Ar 101 and Ar 102 include the substituents represented by R 101 to R 104 described above. The same ring as an aromatic heterocyclic group is mentioned.
  • the aromatic ring itself represented by Ar 101 and Ar 102 has a high T 1 , for example, Benzene ring (including polyphenylene skeletons with multiple benzene rings linked (biphenyl, terphenyl, quarterphenyl, etc.)), fluorene ring, triphenylene ring, carbazole ring, azacarbazole ring, dibenzofuran ring, azadibenzofuran ring, dibenzothiophene ring, dibenzo A thiophene ring, pyridine ring, pyrazine ring, indoloindole ring, indole ring, benzofuran ring, benzothiophene ring, imidazole ring or triazine ring is preferred. More preferred are a benzene ring, a carbazole ring, an
  • Ar 101 and Ar 102 are a carbazole ring or an azacarbazole ring, it is more preferable that they are bonded at the N-position (or 9-position) or the 3-position.
  • Ar 101 and Ar 102 are dibenzofuran rings, they are more preferably bonded at the 2-position or 4-position.
  • each of the aromatic rings represented by Ar 101 and Ar 102 is preferably a condensed ring having three or more rings. .
  • aromatic heterocycle condensed with three or more rings include an acridine ring, an acridan ring, a benzoquinoline ring, a carbazole ring, a carboline ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a carboline ring, Cyclazine ring, quindrine ring, tepenidine ring, quinindrin ring, triphenodithiazine ring, triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (any one of the carbon atoms constituting the carboline ring) Phenanthroline ring, dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring, benzodifuran ring, benzo
  • n101 and n102 are each preferably an integer of 0 to 2, and more preferably n101 + n102 is an integer of 1 to 3. Furthermore, since the R 101 is the n101 and n102 when the hydrogen atom is 0 at the same time, the molecular weight of the host compound represented by the general formula (I) is small, low Tg only be achieved, if R 101 is a hydrogen atom N101 represents an integer of 1 to 4.
  • the carbazole derivative is preferably a compound having a structure represented by the general formula (II). This is because such a compound tends to have particularly excellent carrier transportability.
  • X 101, Ar 101, Ar 102, n102 have the same meanings as X 101, Ar 101, Ar 102 , n102 in each of the general formula (I).
  • N102 is preferably an integer of 0 to 2, more preferably 0 or 1.
  • the condensed ring formed containing X 101 may further have a substituent other than Ar 101 and Ar 102 as long as the function of the host compound used in the present invention is not inhibited. .
  • the compound represented by the general formula (II) is preferably represented by the following general formula (III-1), (III-2) or (III-3).
  • the condensed ring, carbazole ring and benzene ring formed containing X 101 are further substituted within the range not inhibiting the function of the host compound used in the present invention. You may have.
  • examples of host compounds that can be used in the present invention include compounds represented by general formulas (I), (II), (III-1) to (III-3), and other compounds composed of other structures. However, it is not limited to these.
  • the preferred host compound used in the present invention may be a low molecular compound having a molecular weight capable of sublimation purification or a polymer having a repeating unit.
  • the molecular weight is not particularly limited as long as sublimation purification is possible, but the preferred molecular weight is 3000 or less, more preferably 2000 or less.
  • the polymer used as the host compound used in the present invention is not particularly limited as long as the desired device performance can be achieved, but preferably the general formulas (I), (II), (III-1) to (III- What has the structure of 3) in a principal chain or a side chain is preferable.
  • the general formulas (I), (II), (III-1) to (III- What has the structure of 3) in a principal chain or a side chain is preferable.
  • limiting in particular as molecular weight Molecular weight 5000 or more is preferable or a thing with 10 or more repeating units is preferable.
  • 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 glass transition point (Tg) is a value determined by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).
  • the electron transport layer in the present invention 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 in the range of 2 to 500 nm, and still more preferably in the range of 5 to 200 nm. Is within.
  • 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.
  • nitrogen-containing aromatic heterocyclic derivatives (carbazole derivatives, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring are substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, Triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, azatriphenylene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzthiazole derivatives, etc.), dibenzofuran derivatives, Dibenzothiophene derivatives, silole derivatives, aromatic hydrocarbon ring derivatives (naphthalene derivatives, anthracene derivatives, triphenylene derivatives, etc.) It is.
  • a metal complex having a quinolinol skeleton or a dibenzoquinolinol skeleton as a ligand such as tris (8-quinolinol) aluminum (abbreviation: Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,5) 7-dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), and the like
  • Alq 8-quinolinol aluminum
  • Znq 8-quinolinol aluminum
  • a metal complex in which the central metal of the metal complex is replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.
  • metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
  • the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
  • 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 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, azadibenzofurans. Derivatives, azadibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, benzimidazole derivatives, and the like.
  • the electron transport material may be used alone or in combination of two or more.
  • the hole blocking layer is a layer having a function of an electron transport layer in a broad sense, and preferably made of a material having a function of transporting electrons and a small ability to transport holes, while transporting electrons. By blocking holes, the recombination probability of electrons and holes can be improved.
  • the structure of the electron transport layer described above can be used as a hole blocking layer according to the present invention, if necessary.
  • the hole blocking layer 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, and more preferably in the range of 5 to 30 nm.
  • the same materials as those used for the electron transport layer are preferably used, and the materials used as the host compound are also preferably used for the hole blocking layer.
  • the electron injection layer (hereinafter also referred to as “cathode buffer layer”) according to the present invention is a layer provided between a cathode and a light emitting layer for lowering driving voltage and improving light emission luminance. It is described in detail in the second chapter, Chapter 2, “Electrode Materials” (pages 123 to 166) of “Elements and the Forefront of Industrialization (issued by NTT Corporation on November 30, 1998)”.
  • the electron injection layer may be provided as necessary and may exist 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 although depending on the material, the layer thickness is preferably in the range of 0.1 to 5 nm. 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 Metal oxides typified by aluminum, metal complexes typified by lithium 8-hydroxyquinolinate (abbreviation: Liq), and the like can be given. 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 in the range of 2 to 500 nm, and still more preferably in the range of 5 to 200 nm. Within range.
  • a material used for the hole transport layer (hereinafter referred to as a hole transport material), any material that has either a hole injection property or a transport property or an electron barrier property may be used. Any one can be selected and used.
  • porphyrin derivatives for example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives , Indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, and polyvinyl carbazole, polymer materials or oligomers with aromatic amines introduced into the main chain or side chain, polysilane, conductive Polymer or oligomer (for example, PEDOT / PSS, aniline copolymer, polyaniline, polythiophene, etc.)
  • 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: And the same compounds as those used for the hole transport layer described above.
  • 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.
  • Organic layer group in the present invention described above may further contain other additives.
  • 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 group> A method for forming the organic layer group (hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) according to the present invention will be described.
  • the formation method of the organic layer group 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 (N, N-dimethylformamide) and DMSO (dimethylsulfoxide) 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 mes
  • the dispersion can be performed by a method such as ultrasonic dispersion, high shearing force dispersion or media dispersion.
  • the vapor deposition conditions vary depending on the type of compound used, etc., but generally the boat heating temperature is in the range of 50 to 450 ° C., and the degree of vacuum is in the range of 10 ⁇ 6 to 10 ⁇ 2 Pa. It is formed by appropriately selecting a deposition rate within a range of 0.01 to 50 nm / second, a substrate temperature within a range of ⁇ 50 to 300 ° C., and a layer (film) thickness within a range of 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm. It is desirable to do.
  • the formation of the organic layer group according to the present invention is preferably a method of consistently forming from the hole injection layer to the cathode by a single evacuation, but a different film formation method may be applied by taking it out halfway. At that time, the operation is preferably performed in a dry inert gas atmosphere.
  • anode As the anode in the organic EL element, a material having a work function (4 eV or more, preferably 4.5 eV or more) of a metal, an alloy, an electrically conductive compound, or a mixture thereof is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, 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 also be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the anode is usually selected within the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm, although it depends on the applied material.
  • cathode As the cathode, a material having a work function (4 eV or less) metal (hereinafter referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, aluminum, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film from 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.
  • either one of the anode or the cathode of the organic EL element is transparent or translucent because the emission luminance is improved.
  • a transparent or translucent cathode can be produced by producing a conductive transparent material mentioned in the description of the anode on the cathode after producing the above metal with a thickness of 1 to 20 nm.
  • the support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is transparent. Or opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.
  • polyesters such as polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (abbreviation: TAC), cellulose acetate butyrate, Cellulose acetates such as cellulose acetate propionate (abbreviation: CAP), cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, poly Methylpentene, polyetherketone, polyimide, polyethersulfone (abbreviation: PES), polypheny Sulfide, polysulfones, polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyary
  • the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ⁇ 2)% RH) is preferably 0.01 g / m 2 ⁇ 24 h or less, and further, oxygen permeability measured by a method according to JIS K 7126-1987.
  • it is preferably a high-barrier film having 1 ⁇ 10 ⁇ 3 ml / m 2 ⁇ 24 h ⁇ atm or less and a water vapor permeability of 1 ⁇ 10 ⁇ 5 g / m 2 ⁇ 24 h or less.
  • the material for forming the barrier film may be any material that has a function of suppressing the entry of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, and the like can be used.
  • 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 of the organic EL device of the present invention at room temperature (25 ° C.) is preferably 1% or more, and more preferably 5% or more.
  • External extraction quantum efficiency (%) number of photons emitted to the outside of the organic EL element / number of electrons 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 or a metal film can be preferably used from the viewpoint of reducing the thickness of the organic EL element.
  • the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 ml / m 2 ⁇ 24 h ⁇ atm or less, and measured by a method according to JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity 90 ⁇ 2%) is preferably 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ 24 h or less.
  • 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 group on the outer side of the electrode facing the support substrate with the organic layer group interposed therebetween, and form an inorganic or organic layer in contact with the support substrate to form a sealing film.
  • the material for forming the sealing film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • inorganic films such as silicon oxide, silicon dioxide, silicon nitride, etc. Can be used.
  • the sealing film it is preferable to have a laminated structure of these inorganic films and films 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 group 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 method for improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (see, for example, US Pat. No. 4,774,435), A method for improving the efficiency by giving the substrate a light condensing property (for example, see JP-A-63-314795), a method for forming a reflective surface on the side surface of the element (for example, JP-A-1-220394) (See Japanese Laid-Open Patent Publication No. 62-172691), a method of introducing a flat layer having an intermediate refractive index between the substrate and the light emitter to form an antireflection film (see, for example, Japanese Patent Application Laid-Open No.
  • a method of introducing a flat layer having a lower refractive index than the substrate see, for example, Japanese Patent Application Laid-Open No. 2001-202827), any of the substrate, the transparent electrode layer, and the light emitting layer (including the substrate and the outside world). Times) How to form a grating (e.g., see JP Hei 11-283751.) And the like.
  • 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 extraction efficiency increases by diffracting the light traveling in all directions.
  • the position where the diffraction grating is introduced may be in any one of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the light emitting layer where light is generated.
  • the period of the diffraction grating is preferably in the range of about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL element of the present invention is processed to provide, for example, a microlens array-like structure on the light extraction side of the support substrate (substrate), or in combination with a so-called condensing sheet, for example, a specific direction, Condensing light from the front direction with respect to the element light emitting surface can increase luminance in a specific direction.
  • 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, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • BEF brightness enhancement film
  • the shape of the prism sheet for example, the base material may be formed by forming a ⁇ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
  • a light diffusion plate / film may be used in combination with the light collecting sheet.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • 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.
  • a light emitting device for example, a lighting device (for example, household lighting, interior lighting, etc.), a backlight for a clock or a liquid crystal, a billboard advertisement, a traffic light, a light source of an optical storage medium, a light source of an electrophotographic copying machine, an optical communication processor
  • the present invention is not limited to this, but it can be effectively used particularly 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 includes a wiring unit C including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 on the substrate.
  • 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.
  • the power supply line 7 connects the organic EL element 10 to the potential of the image data signal applied to the gate. Current is supplied.
  • the driving of the switching transistor 11 When the scanning signal moves to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, since the capacitor 13 holds the charged potential of the image data signal even when the driving of the switching transistor 11 is turned off, the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues.
  • the driving transistor 12 When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
  • the organic EL element 10 emits light by providing the switching transistor 11 and the driving transistor 12 which are active elements with respect to 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.
  • the organic EL element of the present invention can be applied to 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.
  • One aspect of the lighting device of the present invention One aspect of the lighting device of the present invention that includes the organic EL element of the present invention will be described.
  • 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 (for example, Toagosei Co., Ltd.) is used as a sealing material around Manufactured by LUX TRACK LC0629B), which is stacked on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured, and sealed, as shown in FIGS.
  • a lighting device as shown can be formed.
  • FIG. 6 is a schematic view 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.
  • the sealing operation with the glass cover is performed in a glove box in a nitrogen atmosphere without bringing the organic EL element 101 in the lighting device into contact with the atmosphere, specifically in an atmosphere of high purity nitrogen gas with a purity of 99.999% or more. went.
  • FIG. 7 is a cross-sectional view of the lighting device, 105 is a cathode, 106 is an organic layer group, and 107 is a glass substrate with a transparent electrode (anode).
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • an illumination device having excellent luminous efficiency can be obtained.
  • the light-emitting thin film of the present invention contains a ⁇ -conjugated compound having a structure represented by the general formula (1) according to the present invention, and can be produced in the same manner as the method for forming the organic layer group. it can.
  • the method for forming the light-emitting thin film of the present invention is not particularly limited, and a conventionally known thin film forming method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used.
  • a conventionally known thin film forming 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 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.
  • the dispersion can be performed by a method such as ultrasonic dispersion, 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 degree of vacuum is in the range of 10 ⁇ 6 to 10 ⁇ 2 Pa.
  • the deposition rate is within the range of 0.01 to 50 nm / second
  • the substrate temperature is within the range of ⁇ 50 to 300 ° C.
  • the layer thickness is within the range of 0.1 to 5 ⁇ m, and preferably within the range of 5 to 200 nm. desirable.
  • the 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.
  • the luminescent thin film of the present invention can also be used for display devices and lighting devices.
  • Example 1 Production of organic EL element >> [Production of Organic EL Element 1-1]
  • 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 pressure was reduced to 1 ⁇ 10 ⁇ 4 Pa as the degree of vacuum, and then the energization crucible containing HAT-CN (1, 4, 5, 8, 9, 12-hexaazatriphenylenehexacarbonitrile) was energized and heated. It vapor-deposited on the ITO transparent electrode with the vapor deposition rate of 0.1 nm / sec, and formed the 10-nm-thick hole injection layer.
  • HAT-CN 1, 4, 5, 8, 9, 12-hexaazatriphenylenehexacarbonitrile
  • ⁇ -NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • ⁇ -NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • the hole transport layer was formed.
  • mCBP 3,3-di (9H-carbazol-9-yl) biphenyl
  • the following comparative compound 1 as the light-emitting compound were deposited at a deposition rate of 0 to 90% and 10% by volume, respectively.
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • 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 was covered with a can-shaped glass case in an atmosphere of high purity nitrogen gas having a purity of 99.999% or more, and an electrode lead-out wiring was installed to prepare an organic EL element 1-1.
  • organic EL elements 1-2 to 1-31 were produced in the same manner except that the luminescent compound was changed from the comparative compound 1 to each luminescent compound shown in Table 1. did.
  • the light emission luminance of each organic EL element is measured, and the light emission efficiency at a light emission luminance of 3000 cd / m 2 is obtained.
  • the light emission efficiency (relative value) was determined according to the following formula using the light emission efficiency of the element 1-1 as a reference.
  • Luminous efficiency (relative value) (Luminous efficiency of sample at a luminance of 3000 cd / m 2 / Luminous efficiency of organic EL device 1-1 at a luminance of 3000 cd / m 2 ) ⁇ 100
  • Table 1 shows that the larger the relative value of the light emission efficiency is, the lower the power the element is driven.
  • the drive voltage (relative value) was obtained according to the following equation.
  • Driving voltage (relative value) (initial drive voltage of the light emitting luminance 1000 cd / m 2 initial drive voltage / organic EL element 1-1 in the light emitting luminance 1000 cd / m 2 samples) ⁇ 100
  • Table 1 shows that the smaller the relative value of the voltage value, the better the conductivity of the element, and that the element is driven at a low voltage. Table 1 shows the results obtained as described above.
  • Example 2 Production of organic EL element >> [Production of Organic EL Element 2-1]
  • a transparent support substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) in which ITO (indium tin oxide) was formed as a positive electrode on a 100 mm ⁇ 100 mm glass substrate having a thickness of 1.1 mm was subjected to patterning treatment. Thereafter, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (abbreviation: PEDOT / PSS, Bayer, Baytron PAl 4083) to 70% with pure water was used.
  • PEDOT / PSS polystyrene sulfonate
  • a thin film was formed by spin coating under the conditions of 3000 rpm and 30 seconds, and then dried at 200 ° C. for 1 hour to form 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 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • H-46 which is an exemplary compound
  • comparative compound 2 were co-deposited at a deposition rate of 0.1 nm / second under the conditions of 94% and 6% by volume, respectively, and a light emitting layer having a layer thickness of 30 nm Formed.
  • TPBi 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene) was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a layer thickness of 30 nm.
  • the non-light emitting surface side of the organic EL element is covered with a can-shaped glass case in an atmosphere of high-purity nitrogen gas with a purity of 99.999% or more, and an electrode lead-out wiring is installed to produce an organic EL element 2-1. did.
  • Table 2 shows the results obtained as described above.
  • the organic EL elements 2-4 to 2-11 of the present invention have higher luminous efficiency than the organic EL elements 2-1 to 2-3 of Comparative Examples. Obviously. This is considered to be the effect that the compound according to the present invention assists the emission of other fluorescent compounds. That is, when the fluorescent compound according to the present invention having a higher energy level than the luminescent material is excited in the light emitting device, the luminescent material efficiently receives the energy, whereby the compound according to the present invention emits light. It is thought that luminous efficiency comparable to that can be obtained.
  • Example 3 When a toluene solution of Exemplified Compound D15 according to the present invention was prepared and irradiated with light at 280 nm at 300 K while bubbling nitrogen, green light emission was observed.
  • this exemplary compound D15 components having a long emission lifetime were observed in addition to ns order fluorescence.
  • the time-resolved spectrum was measured with a fluorescence lifetime measuring device Quantaurus-tau manufactured by Hamamatsu Photonics Co., Ltd., and the component having a short emission lifetime was determined to be fluorescence. The long component was judged as delayed fluorescence.
  • Example 4 Production of organic EL element >> (Preparation of organic EL element 4-1) 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 apparatus was filled with an optimum amount of the constituent material of each layer for manufacturing each element.
  • the resistance heating boat was made of molybdenum or tungsten.
  • ⁇ -NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • a resistance heating boat containing comparative compound 4 as a host compound and GD-1 as a luminescent compound is energized and heated, and the hole transport is performed at a deposition rate of 0.1 nm / second and 0.010 nm / second, respectively.
  • a light-emitting layer having a thickness of 40 nm was formed by co-evaporation on the layer.
  • Exemplary Compound H-42 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.
  • sodium fluoride was vapor-deposited so as to have a thickness of 0.5 nm, and then aluminum was vapor-deposited with a thickness of 100 nm to form a cathode, thereby producing an organic EL element 4-1.
  • Organic EL devices 4-2 to 4-11 were fabricated in the same manner as the organic EL device 4-1, except that the host compound used for forming the light emitting layer was changed to each compound shown in Table 3.
  • the organic EL elements 4-2 to 4-11 have a lower driving voltage and excellent luminous efficiency than the organic EL element 4-1 as a comparative example. I understand.
  • the compound according to the present invention is also effective as a host material. That is, it is presumed that the compound according to the present invention is excellent in carrier transportability and can assist in light emission of the dopant.
  • the organic electroluminescence device of the present invention can achieve a high luminous efficiency with a reduced driving voltage, and can be suitably used for a light-emitting thin film, a display device, and a lighting device containing a conjugated compound according to the present invention.

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  • Electroluminescent Light Sources (AREA)
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  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

La présente invention aborde le problème de la réalisation d'un élément électroluminescent organique qui possède une faible tension d'attaque et qui permet d'obtenir un rendement d'émission de lumière élevé. L'invention concerne en outre : un film mince émetteur de lumière qui contient un composé conjugué selon la présente invention ; et un dispositif d'affichage ainsi qu'un dispositif d'éclairage qui sont pourvus de l'élément électroluminescent organique. L'élément électroluminescent organique selon l'invention est caractérisé en ce qu'il comprend, entre une anode et une cathode, un groupe de couches organiques incluant au moins une couche émettrice de lumière. Au moins une couche dudit groupe de couches organiques contient un composé conjugué π ayant une structure représentée par la formule générale (1). [Dans la formule, A représente un groupe attracteur d'électrons, et D représente un groupe donneur d'électrons. m et n représentent chacun indépendamment des nombres entiers 1 ou 2. X représente un groupe d'hydrocarbone aromatique sélectionné à partir d'une structure représentée par une structure spécifique.]
PCT/JP2015/070917 2014-07-31 2015-07-23 Élément électroluminescent organique, film mince émetteur de lumière, dispositif d'affichage et dispositif d'éclairage WO2016017514A1 (fr)

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