WO2015029964A1 - Élément à électroluminescence organique, matériau électroluminescent, pellicule mince électroluminescente, dispositif d'affichage et dispositif d'éclairage - Google Patents

Élément à électroluminescence organique, matériau électroluminescent, pellicule mince électroluminescente, dispositif d'affichage et dispositif d'éclairage Download PDF

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WO2015029964A1
WO2015029964A1 PCT/JP2014/072224 JP2014072224W WO2015029964A1 WO 2015029964 A1 WO2015029964 A1 WO 2015029964A1 JP 2014072224 W JP2014072224 W JP 2014072224W WO 2015029964 A1 WO2015029964 A1 WO 2015029964A1
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organic
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light
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池水　大
押山　智寛
秀雄 ▲高▼
北　弘志
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コニカミノルタ株式会社
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Definitions

  • the present invention relates to an organic electroluminescence element and a light emitting material.
  • the present invention also relates to a light-emitting thin film containing the light-emitting material, a display device and a lighting device including the organic electroluminescence element, the light-emitting material, or the light-emitting thin film. More specifically, the present invention relates to an organic electroluminescence element with improved luminous efficiency.
  • Organic EL elements also referred to as “organic electroluminescent elements” using electroluminescence of organic materials (Electro Luminescence: hereinafter abbreviated as “EL”) have already been put into practical use as a new light emitting system that enables planar light emission.
  • EL Electro Luminescence
  • organic EL emission methods There are two types of organic EL emission methods: “phosphorescence emission” that emits light when returning from the triplet excited state to the ground state and “fluorescence emission” that emits light when returning from the singlet excited state to the ground state. There is.
  • phosphorescence emission that emits light when returning from the triplet excited state to the ground state
  • fluorescence emission that emits light when returning from the singlet excited state to the ground state.
  • quantum yield in the phosphorescence emission method, it is necessary to use a complex using a rare metal such as iridium or platinum as a central metal, In addition, there is concern that the reserves of rare metals and the price of the metals themselves will be a major issue in the industry.
  • the TADF mechanism is a compound having a smaller difference ( ⁇ Est) between the singlet excitation energy level and the triplet excitation energy level ( ⁇ Est (TADF) in FIG. 1) as compared with a normal fluorescent compound. Is smaller than ⁇ Est (F).), A light emission mechanism utilizing a phenomenon in which a reverse intersystem crossing from a triplet exciton to a singlet exciton occurs.
  • some of the conventional fluorescent luminescent compounds including the fluorescent luminescent compound using the TADF mechanism exhibit the property of aggregating, and the aggregation is seen on the longer wavelength side than the emission wavelength indicated by one molecule. It is known that there are those that emit excimer light. When the fluorescent compound emits excimer light, the light emission intensity is lowered, which may lead to a decrease in light emission efficiency. Further, as a characteristic of the fluorescent light-emitting compound itself, there is a problem that the charge transport property is biased, and in particular, when the charge transport property is poor, the light emission efficiency is similarly reduced.
  • the present inventor in the electron density distribution of the fluorescent compound obtained by structural optimization calculation using a semi-empirical molecular orbital calculation method
  • the present inventors have found that the luminous efficiency is improved when the distance between the centers of the highest occupied orbit (HOMO) and the lowest empty orbit (LUMO) is in the range of 5.0 to 9.0 mm. That is, the said subject which concerns on this invention is solved by the following means.
  • An organic electroluminescence device having at least one organic layer including an organic layer containing a fluorescent compound between a pair of electrodes, The distance between centers of the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) in the electron density distribution of the fluorescent compound obtained by structural optimization calculation using a semi-empirical molecular orbital calculation method is 5.
  • An organic electroluminescence device characterized by being in the range of 0 to 9.0 mm.
  • the longest distance from the molecular center of the lowest unoccupied orbital (LUMO) in the electron density distribution of the fluorescent compound obtained by structural optimization calculation using the semiempirical molecular orbital calculation method is the semiempirical molecule.
  • a host compound having a structure represented by the following general formula (I) is contained:
  • 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.
  • 101 to R 104 each represent a hydrogen atom or a substituent, and may be bonded to each other to form a ring, and Ar 101 and Ar 102 each represent an aromatic ring, and may be the same or different.
  • n101 and n102 each represents an integer of 0 to 4, but when R 101 is a hydrogen atom, n101 represents an integer of 1 to 4.
  • the center-to-center distance between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) in the electron density distribution obtained by the structural optimization calculation using the semi-empirical molecular orbital calculation method is 5.0 to 9.0 mm.
  • the longest distance from the molecular center of the lowest unoccupied orbital (LUMO) in the electron density distribution obtained by structural optimization calculation using the semiempirical molecular orbital calculation method is calculated by the semiempirical molecular orbital calculation method. 6.
  • Item 7 The light-emitting material according to Item 5 or 6, which contains a host compound having a structure represented by the following general formula (I) in addition to the fluorescent compound.
  • 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.
  • 101 to R 104 each represent a hydrogen atom or a substituent, and may be bonded to each other to form a ring, and 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.
  • a luminescent thin film comprising the luminescent material according to any one of items 5 to 8.
  • a display device comprising the organic electroluminescence element according to any one of items 1 to 4.
  • a display device comprising the luminescent material according to any one of items 5 to 8.
  • a light-emitting thin film according to item 9 is used.
  • the above-mentioned means of the present invention can provide an organic electroluminescence element and a light emitting material capable of improving the light emission efficiency.
  • a light-emitting thin film containing the light-emitting material and a display device and a lighting device including the organic electroluminescent element, the light-emitting material, or the light-emitting thin film can be provided.
  • the expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
  • the present inventors have found that the center of the highest occupied orbital (HOMO) and the lowest empty orbital (LUMO) in the ground state of the fluorescent compound. It was found that excimer luminescence was observed when the distance was away from a certain distance, and the decrease in luminescence intensity was noticeable.
  • the distance from the molecular center of the lowest unoccupied orbital (LUMO) is shorter than the van der Waals radius in the re-stabilized structure of the ground state of the fluorescent compound, and the distance from the molecular center of the highest occupied orbital (HOMO) It has also been found that when the distance is longer than the van der Waals distance, the charge transport property is biased, and particularly the electron transport property is significantly reduced.
  • HOMO and LUMO are separated.
  • a molecule having both a donor site and an acceptor site in the molecule In such a case, HOMO is often localized at the donor site, and LUMO is often localized at the acceptor site.
  • HOMO and LUMO are located at both ends of the molecule. Will exist.
  • the organic molecule is synonymous with performing its own charge during the HOMO-LUMO transition, that is, it can be said that the intramolecular charge transfer (CT) property is strong.
  • CT intramolecular charge transfer
  • Such a molecule has a large bias in charge density within the molecule itself, and it is considered that the donor and the acceptor site are close to each other by electrostatic attraction, and an aggregate is easily formed. It is considered that stable low energy levels are formed by forming aggregates, which leads to excimer emission.
  • the organic molecule is a fluorescent compound that undergoes a triplet, that is, a TADF compound
  • the triplet component is deactivated by forming an aggregate, which may lead to a decrease in the emission quantum yield.
  • the molecule is a spherical molecule.
  • HOMO is present at the end of the molecule, and LUMO is close to the center of the molecule.
  • the LUMO is hidden inside the HOMO of the spherical molecule, and in the latter case, the LUMO is hidden in a substituent that does not participate in light emission outside the LUMO.
  • a fluorescent compound is used in an electronic device such as an organic EL element, holes can smoothly move (hop) through the HOMO level of the molecule, but LUMO is hidden inside the molecule. Therefore, it is considered that electron hopping is prevented as compared with holes, and as a result, the charge transport property is biased. Therefore, it is possible to provide an organic EL device with improved luminous efficiency by suppressing aggregation of the fluorescent compound and improving charge transportability.
  • a light-emitting thin film containing the light-emitting material and a display device and a lighting device including the organic electroluminescent element, the light-emitting material, or the light-emitting thin film can be provided.
  • Schematic diagram showing energy diagrams of normal fluorescent compounds and TADF compounds Schematic diagram showing an example of a display device composed of organic EL elements
  • Schematic diagram of an active matrix display device Schematic showing the pixel circuit
  • Schematic diagram of a passive matrix display device Schematic of lighting device
  • An organic electroluminescence device having at least one organic layer including an organic layer containing a fluorescent compound between a pair of electrodes,
  • the distance between centers of the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) in the electron density distribution of the fluorescent compound obtained by structural optimization calculation using a semi-empirical molecular orbital calculation method is 5. It is characterized by being in the range of 0 to 9.0 mm. This feature is a technical feature common to the inventions according to claims 1 to 15.
  • the longest distance from the molecular center of the lowest unoccupied orbital (LUMO) in the electron density distribution of the fluorescent compound obtained by structural optimization calculation using the semiempirical molecular orbital calculation method is the semiempirical value.
  • the electron mobility in the organic EL device is improved, and accordingly, the light emission efficiency at the high current density in the organic EL device is decreased. Since the effect of roll-off improvement is acquired, it is preferable.
  • At least one of the organic layers contains a host compound having a structure represented by the general formula (I) in addition to the fluorescent compound. Is preferable.
  • the host compound having the structure represented by the general formula (I) preferably has the structure represented by the general formula (II).
  • the good interaction between the host compound and the dopant compound improves the cohesiveness of the molecules and enables good charge transfer, so the effect obtained by the fluorescent compound can be synergistically improved.
  • the effect of improving the luminous efficiency and half-life can be obtained.
  • the center-to-center distance between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) in the electron density distribution obtained by structural optimization calculation using a semi-empirical molecular orbital calculation method. Is characterized by containing a fluorescent compound that is in the range of 5.0 to 9.0 mm.
  • the longest distance from the molecular center of the lowest unoccupied orbital (LUMO) in the electron density distribution obtained by structural optimization calculation using the semiempirical molecular orbital calculation method It is preferable to contain a fluorescent compound having a size that is 0.1 mm or more larger than the van der Waals radius calculated by the semi-empirical molecular orbital calculation method.
  • a host compound having a structure represented by the general formula (I) in order to further enhance the effects of the present invention.
  • the host compound having the structure represented by the general formula (I) it is preferable for the host compound having the structure represented by the general formula (I) to have the structure represented by the general formula (II) in order to further enhance the effects of the present invention.
  • the luminescent material of the present invention can be suitably provided for a luminescent thin film. Thereby, a luminescent thin film with improved luminous efficiency is obtained.
  • the organic electroluminescence element of the present invention can be suitably provided in a display device. As a result, a display device with improved luminous efficiency and half life can be obtained.
  • the light emitting material of the present invention can be suitably included in a display device. As a result, a display device with improved luminous efficiency and half life can be obtained.
  • the luminescent thin film of the present invention can be suitably provided in a display device. As a result, a display device with improved luminous efficiency and half life can be obtained.
  • the organic electroluminescence element of the present invention can be suitably provided in a lighting device. Thereby, the illuminating device with improved luminous efficiency and half life can be obtained.
  • the luminescent material of the present invention can be suitably included in a lighting device. Thereby, the illuminating device with improved luminous efficiency and half life can be obtained.
  • the luminescent thin film of the present invention can be suitably provided in a lighting device. Thereby, the illuminating device with improved luminous efficiency and half life can be obtained.
  • Organic EL emission methods There are two types of organic EL emission methods: “phosphorescence emission” that emits light when returning from the triplet excited state to the ground state, and “fluorescence emission” that emits light when returning from the singlet excited state to the ground state. is there.
  • phosphorescence emission that emits light when returning from the triplet excited state to the ground state
  • fluorescence emission that emits light when returning from the singlet excited state to the ground state.
  • TTA triplet-triplet annealing
  • the rate constant is usually small. That is, since the transition is difficult to occur, the exciton lifetime is increased from millisecond to second order, and it is difficult to obtain desired light emission.
  • the rate constant of the forbidden transition increases by 3 digits or more due to the heavy atom effect of the central metal. % Phosphorescence quantum yield can be obtained.
  • a rare metal called a white metal such as iridium, palladium, or platinum, which is a rare metal. The price of the metal itself is a major industrial issue.
  • a general fluorescent compound is not necessarily a heavy metal complex like a phosphorescent compound, and is a so-called organic compound composed of a combination of general elements such as carbon, oxygen, nitrogen, and hydrogen.
  • other non-metallic elements such as phosphorus, sulfur, and silicon can be used, and complexes of typical metals such as aluminum and zinc can be used.
  • high efficiency light emission such as phosphorescence emission cannot be expected.
  • TTA triplet-triplet annihilation
  • Thermal activated delayed fluorescence (TADF) compound which is another highly efficient fluorescent emission, is a method that can solve the problems of TTA.
  • the fluorescent compound has the advantage that it can be designed indefinitely. That is, among the molecularly designed compounds, there are compounds in which the absolute value of the energy level difference between the triplet excited state and the singlet excited state (hereinafter referred to as ⁇ Est) is extremely close (see FIG. 1). Although such a compound does not have a heavy atom in the molecule, a reverse intersystem crossing from a triplet excited state to a singlet excited state, which cannot normally occur due to a small ⁇ Est, occurs.
  • TADF can ideally emit 100% fluorescence.
  • Non-Patent Document 1 by introducing an electron-withdrawing skeleton such as a cyano group, a sulfonyl group, or triazine and an electron-donating skeleton such as a carbazole or diphenylamino group, LUMO and HOMO Are localized. It is also effective to reduce the change in molecular structure between the ground state and triplet excited state of the compound. As a method for reducing the structural change, for example, making the compound rigid is effective.
  • Rigidity described here means that there are few sites that can move freely in the molecule, for example, by suppressing free rotation in the bond between rings in the molecule or by introducing a condensed ring with a large ⁇ conjugate plane. means. In particular, it is possible to reduce the structural change in the excited state by making the portion involved in light emission rigid.
  • TADF compounds have various problems in terms of their light emission mechanism and molecular structure. The following describes some of the problems generally associated with TADF compounds.
  • the electronic state of the molecule is a donor / acceptor type molecule in which the HOMO and LUMO sites are separated. It becomes a state close to the inner CT (intramolecular charge transfer state).
  • 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 or five molecules, resulting in various stable distributions with a wide distribution. Therefore, the shape of the absorption spectrum and the emission spectrum is broad. In addition, even when a multimolecular assembly exceeding two molecules is not formed, 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 creates two major problems.
  • One problem is that the color purity of the emitted color is lowered. This is not a big problem when applied to lighting applications, but when used for electronic displays, the color gamut is small and the color reproducibility of pure colors is low. It becomes difficult.
  • fluorescence zero-zero band the rising wavelength (referred to as “fluorescence zero-zero band”) on the short wavelength side of the emission spectrum is shortened, that is, the S 1 is increased (the lowest excitation singlet energy is increased). It is to end.
  • 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. This is a very big problem.
  • 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.
  • 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. As a result, the reverse reverse energy transfer from the triplet excited state to the singlet excited state of the originally intended TADF compound does not occur sufficiently, and unfavorable reverse energy transfer to the host compound becomes the mainstream, resulting in sufficient luminous efficiency. Inconvenience that cannot be obtained.
  • the present invention includes, as a design concept, a fluorescent compound that suppresses the structural change in the excited state as described above and a fluorescent compound that has a short triplet excited state.
  • a fluorescent compound that suppresses the structural change in the excited state as described above and a fluorescent compound that has a short triplet excited state.
  • HOMO and LUMO are substantially separated in the molecule from the viewpoint of reducing ⁇ Est.
  • the distribution states of these HOMO and LUMO can be obtained from the electron density distribution when the structure is optimized obtained by semi-empirical molecular orbital calculation.
  • the structure optimization and the calculation of the electron density distribution by the semi-empirical molecular orbital calculation of the fluorescent compound in the present invention are carried out using a molecular orbital calculation using B3LYP as a functional and 6-31G (d) as a basis function.
  • B3LYP as a functional and 6-31G (d) as a basis function.
  • 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.
  • the separation state of HOMO and LUMO from the above-mentioned structure optimization calculation using B3LYP as the functional and 6-31G (d) as the basis function, the time-dependent density functional method (Time-Dependent DFT) is used.
  • ⁇ Est is smaller, HOMO and LUMO are more separated.
  • ⁇ Est calculated using the same calculation method as described above is preferably 0.5 eV or less, more preferably 0.2 eV or less, and further preferably 0.1 eV or less.
  • the highest occupied orbit (HOMO) and the lowest unoccupied orbit (LUMO) according to the present invention are calculated by molecular orbital calculation. That is, the structure optimization and the calculation of the electron density distribution by the semi-empirical molecular orbital calculation method of the fluorescent compound in the present invention are B3LYP as a functional, 6-31G (d) as a basis function, or a general function. It can be calculated using molecular orbital calculation software using M06-2X as a function and 6-31G (d) as a basis function, and there is no particular limitation on the software, and any of them can be similarly obtained. .
  • Gaussian 09 (Revision C.01, MJ Frisch, et al, Gaussian, Inc., 2010.) manufactured by Gaussian, USA was used as molecular orbital calculation software. Winstar, available as free software, was used to display the coordinates of the optimized structure and the highest occupied orbit (HOMO) and lowest empty orbit (LUMO).
  • the HOMO and LUMO calculated by the semi-empirical molecular orbital calculation method use the optimized structure of the ground state (S 0 ).
  • the distance between the centers of HOMO and LUMO is defined as follows.
  • the center of the molecule is determined as the origin in XYZ coordinates.
  • a group of constituent atoms having the highest electron density displayed as HOMO is defined as a three-dimensional region having a volume corresponding to the electron density distribution, and the center coordinates of the three-dimensional region are calculated.
  • An intermediate point between the center of the molecule determined as the origin and the center coordinate of the three-dimensional region corresponding to the electron density distribution is calculated and defined as a.
  • the center coordinates of the three-dimensional region corresponding to the electron density distribution are calculated for a group of constituent atoms having the highest electron density displayed as LUMO, and the center of the molecule and the tertiary corresponding to the electron density distribution are calculated.
  • the middle point of the center coordinates of the original area is defined as b.
  • a distance obtained by connecting a and b with a straight line is defined as a center-to-center distance between HOMO and LUMO.
  • the average value of the distances connecting the distances a and b between the centers is defined as the distance between the centers of HOMO and LUMO.
  • the intermediate points a and b when the intermediate points a and b are deviated from the coordinates where atoms in the molecule exist, the intermediate points a and b can be approximated to a and b, respectively, by the atoms at the shortest distance from the coordinates.
  • the highest occupied orbit (HOMO) and the lowest unoccupied orbit (in the electron density distribution of the fluorescent compound obtained by structure optimization calculation using a semi-empirical molecular orbital calculation method is within the range of 5.0 to 9.0 mm.
  • the distance between the centers of HOMO and LUMO in the electron density distribution of the fluorescent compound is within the range of 5.0 to 9.0 mm.
  • the distance between the centers of HOMO and LUMO in the electron density distribution of the fluorescent compound is in the range of 5.5 to 7.5 mm.
  • the longest distance from the center of gravity of the lowest empty orbit (LUMO) is obtained by determining the distance between the aforementioned molecular center and the atom at the longest distance among a group of atoms with the highest electron density displayed as LUMO. .
  • VDW radius The van der Waals radius of a molecule can be obtained from the van der Waals volume of the molecule by the following formula when a structure optimized by the molecular calculation method is displayed by Winmoster.
  • V 4/3 ⁇ ⁇ r 3
  • V the van der Waals volume
  • r the van der Waals radius.
  • the longest distance from the molecular center of the lowest orbital (LUMO) in the electron density distribution of the fluorescent compound obtained by structural optimization calculation using a semi-empirical molecular orbital calculation method is The radius is preferably 0.1 mm or more larger than the van der Waals radius calculated by the semi-empirical molecular orbital calculation method.
  • the lowest excited singlet energy S 1 of the fluorescent compound in the present invention is defined in the present invention as calculated in the same manner as in a normal method. That is, a sample to be measured is deposited on a quartz substrate to prepare a sample, and the absorption spectrum (vertical axis: absorbance, horizontal axis: wavelength) of this sample is measured at room temperature (300 K). A tangent line is drawn with respect to the rising edge of the absorption spectrum on the long wavelength side, and is calculated from a predetermined conversion formula based on the wavelength value at the intersection of the tangent line and the horizontal axis.
  • the aggregation property of the molecule of the fluorescent compound used in the present invention is relatively high, an error due to aggregation may occur in the measurement of the thin film.
  • the lowest excited singlet energy S 1 in the present invention is at room temperature (25 ° C.). The peak value of the maximum emission wavelength in the solution state of the fluorescent compound was used as an approximate value.
  • 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 fluorescent compound in the present invention was calculated from the photoluminescence (PL) characteristics of the solution or thin film.
  • PL photoluminescence
  • the lowest excited triplet energy can be obtained from the lowest excited singlet energy with the energy difference as ⁇ Est.
  • an absolute PL quantum yield measuring apparatus C9920-02 manufactured by Hamamatsu Photonics
  • the light emission lifetime was measured using a streak camera C4334 (manufactured by Hamamatsu Photonics) while exciting the sample with laser light.
  • the light emitting layer according to 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 according to 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 according to the present invention is a layer having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. Moreover, you may be comprised by multiple layers. In the above-described typical element configuration, the layer excluding the anode and the cathode is also referred to as “organic layer”.
  • the organic EL element of the present invention may be a so-called tandem element in which a plurality of light emitting units including at least one light emitting layer are stacked.
  • a tandem element in which a plurality of light emitting units including at least one light emitting layer are stacked.
  • the first light emitting unit, the second light emitting unit and the third light emitting unit are all the same, May be different.
  • Two light emitting units may be the same, and the remaining one may be different.
  • a plurality of light emitting units may be laminated directly or via an intermediate layer, and the intermediate layer is generally an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, an intermediate layer.
  • a known material structure can be used as long as it is also called an insulating layer and has a function of supplying electrons to the anode-side adjacent layer and holes to the cathode-side adjacent layer.
  • Examples of materials used for the intermediate layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO 2 , TiN, ZrN, HfN, TiOx, VOx, CuI, InN, GaN, and CuAlO 2.
  • 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.
  • JP-A-2006-228712 JP-A-2006-24791, JP-A-2006-49393, JP-A-2006-49394 JP-A-2006-49396, JP-A-2011-96679, JP-A-2005-340187, JP-A-4711424, JP-A-34968681, JP-A-3884564, JP-A-42131169, JP-A-2010-192719.
  • Examples include constituent materials, but the present invention is not limited to these.
  • the light emitting layer according to 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 a layer of the light emitting layer. Even within, it may be the interface between the light emitting layer and the adjacent layer.
  • the structure of the light emitting layer according to the present invention is not particularly limited as long as it satisfies the requirements defined in the present invention.
  • the total thickness of the light emitting layer is not particularly limited, but it prevents the uniformity of the film to be formed, the application of unnecessary high voltage during light emission, and the improvement of the stability of the emission color against the drive current.
  • each light emitting layer according to the present invention is preferably adjusted to a range of 2 nm to 1 ⁇ m, more preferably adjusted to a range of 2 to 200 nm, and further preferably adjusted to a range of 3 to 150 nm. Is done.
  • the light-emitting layer according to 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 includes the aforementioned host compound (a matrix material, a light-emitting host compound, or simply a host). It is 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 aforementioned host compound a matrix material, a light-emitting host compound, or simply a host. It is 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
  • the light emitting layer contains the fluorescent compound in the range of 5 to 40% by mass, and particularly preferably in 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 specific fluorescent compound 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 and may have any concentration distribution.
  • the fluorescent compound according to the present invention may be used in combination of two or more kinds, a combination of fluorescent compounds having different structures, or a combination of a fluorescent compound and a phosphorescent compound. May be. Thereby, arbitrary luminescent colors can be obtained.
  • the light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 3.16 on page 108 of “New Color Science Handbook” (edited by the Japan Society of Color Science, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total of CS-1000 (manufactured by Konica Minolta Co., Ltd.) is applied to the CIE chromaticity coordinates.
  • the light emitting layer of one layer or a plurality of layers contains a plurality of light emitting dopants having different emission colors and emits white light.
  • the fluorescent compound according to the present invention is preferably a fluorescent compound having a structure represented by the following general formula (1).
  • Ar represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group which may be condensed, and at least one place is substituted with Q.
  • n represents a natural number. When n is 2 or more, each Ar may be different.
  • Q represents an electron donating group or an electron accepting group.
  • L represents a divalent linking group.
  • m represents a natural number, and when m is 2 or more, each L may be different.
  • p represents a natural number, and when p is 2 or more, each of Ar, Q and L may be different.
  • a fluorescent compound having a structure represented by the following general formula (2) is preferable.
  • Ar and Ar ′ represent an aromatic hydrocarbon ring group having a substituent which may be condensed or an aromatic heterocyclic group having a substituent.
  • Ar and Ar ′ may be different.
  • R represents a methyl group or a phenyl group.
  • a fluorescent compound having a structure represented by the following general formula (3) is preferable.
  • R 1 , R 2 , R 3 and R 4 each represent a hydrogen atom, a branched alkyl group, an aryl group, a heteroaryl group or a cyano group.
  • X 1 to X 4 each represents a sulfur atom, a sulfinyl group or a sulfonyl group.
  • the fluorescent compound preferably has an aromatic hydrocarbon ring group or an aromatic heterocyclic group derived from the following compounds represented by Ar-1 to Ar-8 as Ar.
  • R ′ represents an alkyl group, an aryl group or a heteroaryl group.
  • the fluorescent compound has an aromatic hydrocarbon ring group or an aromatic heterocyclic group derived from the compound having a structure represented by Ar-1 to Ar-8 as the Ar ′.
  • the fluorescent compound represented by the general formula (3) preferably used in the present invention will be given below, but the present invention is not limited thereto.
  • the fluorescent compound represented by the general formula (3) represents a compound in which X 1 to X 4 and R 1 to R 4 are substituted with the elements described in Tables 1 and 2.
  • Cz represents a carbazolyl group.
  • the compound represented by the general formula (1) can be synthesized by using a known synthesis reaction such as an experimental chemistry course (edited by the Chemical Society of Japan).
  • a known synthesis reaction such as an experimental chemistry course (edited by the Chemical Society of Japan).
  • the compound represented by the general formula (2) is described in Chem. Lett. , 2012, 1652 and the like.
  • the fluorescent compound according to the present invention includes a 5-membered or 6-membered aromatic heterocycle containing 1 or 2 nitrogen atoms or a condensed aromatic heterocycle containing the 5-membered or 6-membered aromatic heterocycle in the skeleton.
  • a compound represented by the following general formula (A) having an electron-withdrawing group and a monocyclic or condensed ring group as the electron-donating group is preferable.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • the linking site represented by Ar 0 may be anything as long as it does not inhibit the function of the compound of the general formula (A), and is preferably an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a combination thereof. It is.
  • EWG represents a 5-membered or 6-membered aromatic heterocycle containing 1 or 2 nitrogen atoms, or a condensed aromatic heterocycle containing the 5-membered or 6-membered aromatic heterocycle in the skeleton. Represents an electron-withdrawing group.
  • Examples of the electron-withdrawing group include those shown as the following 6 ⁇ -type electron withdrawing group, 10 ⁇ -type electron withdrawing group, and 14 ⁇ -type electron withdrawing group.
  • the 6 ⁇ electron-withdrawing group is a 5- or 6-membered heterocyclic group containing a nitrogen atom.
  • examples thereof include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, and a furazane ring.
  • Preferable examples include a pyridine ring, a pyrimidine ring, a pyridazine ring, and a pyrazine ring.
  • the electron-withdrawing group of 10 ⁇ electron system is a condensed ring compound consisting of 5 or 6 members containing a nitrogen atom.
  • Examples include indole ring, indazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, isoindole ring, naphthyridine ring, phthalazine ring and the like.
  • a benzothiazole ring, a benzoxazole ring, and a benzimidazole ring are mentioned.
  • the electron-withdrawing group of 14 ⁇ electron system is a 5- or 6-membered condensed ring compound containing a nitrogen atom.
  • a carbazole ring, carboline ring, diazacarbazole ring in which one of the carbon atoms constituting the carboline ring is replaced by a nitrogen atom
  • acridine ring phenanthridine ring, phenanthroline ring, phenazine ring, azadibenzofuran Ring, azadibenzothiophene ring and the like.
  • a carboline ring, a diazacarbazole ring, an azadibenzofuran ring, and an azadibenzothiophene ring are mentioned.
  • EDG represents a monocyclic or condensed ring group which is an electron donating group.
  • carbazole ring, thiophene ring, pyrrole ring, mesityl group, xylyl group and the like can be mentioned.
  • m and n represent an integer of 1 to 6.
  • X 11 , X 12 , X 13 , X 14 and X 15 each independently represent a nitrogen atom or CRa, but X 11 , X 12 , X 13 , X 14 and X 15 One or two of them represent a nitrogen atom.
  • Ra represents a hydrogen atom or a substituent.
  • substituents include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, Octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl) Group, propargyl group, etc.), aromatic hydrocarbon group (aromatic hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc.
  • alkyl group for example, a methyl group, an ethyl
  • substituents may be further substituted with the above substituents. Further, these substituents may be bonded together to form a ring.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • EDG represents a monocyclic or condensed ring group which is an electron donating group.
  • n and n represent an integer of 1 to 6.
  • X 21 represents NRb, C (Rc) (Rd), an oxygen atom or a sulfur atom.
  • X 22 , X 23 , X 24 , X 25 and X 26 each independently represent a nitrogen atom or CRa.
  • X 21 , X 22 , X 23 , X 24 , X 25 and X 26 represent a nitrogen atom.
  • Ra, Rb, Rc and Rd each independently represent a hydrogen atom or a substituent.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • EDG represents a monocyclic or condensed ring group which is an electron donating group.
  • m and n each represents an integer of 1 to 6.
  • X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , X 37 and X 38 each independently represent a nitrogen atom or CRa.
  • One or two of X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , X 37 and X 38 represent a nitrogen atom.
  • Ra represents a hydrogen atom or a substituent.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • EDG represents a monocyclic or condensed ring group which is an electron donating group.
  • m and n represent an integer of 1 to 6.
  • X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , X 37 and X 38 each independently represent a nitrogen atom or CRa.
  • One or two of X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , X 37 and X 38 represent a nitrogen atom.
  • R 1 and Ra represent a hydrogen atom or a substituent.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • EDG represents a monocyclic or condensed ring group which is an electron donating group.
  • m and n each represents an integer of 1 to 6.
  • R 1 and Ra represent a substituent
  • the substituent has the same meaning as Ra in the general formula (1-1).
  • substitution position of Ar 0 , X 35 or X 37 is preferable.
  • X 31, X 32, X 33, X 34, X 35, X 36 and X 38 each independently represent a nitrogen atom or CRa.
  • One or two of X 31 , X 32 , X 33 , X 34 , X 35 , X 36 and X 38 represent a nitrogen atom.
  • R 2 and Ra represent a hydrogen atom or a substituent.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • EDG represents a monocyclic or condensed ring group which is an electron donating group.
  • m and n each represents an integer of 1 to 6.
  • X 11 , X 12 , X 13 , X 14 and X 15 each independently represent a nitrogen atom or CRa, but X 11 , X 12 , X 13 , X 14 and X 15 One or two of them represent a nitrogen atom.
  • Ra represents a hydrogen atom or a substituent.
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom or a substituent.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • m and n represent an integer of 1 to 6.
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 and Ra represent a substituent
  • the substituent may be represented by the general formula (1 It is synonymous with Ra in -1).
  • X 21 , X 22 , X 23 , X 24 , X 25 and X 26 each independently represent a nitrogen atom, NRb, an oxygen atom, a sulfur atom or CRa.
  • One or two of X 21 , X 22 , X 23 , X 24 , X 25 and X 26 represent a nitrogen atom.
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 are each independently a hydrogen atom or a substituent.
  • Ra and Rb represent a hydrogen atom or a substituent.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • m and n represent an integer of 1 to 6.
  • X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , X 37 and X 38 in the general formula (3-4) each independently represent a nitrogen atom or CRa.
  • One or two of X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , X 37 and X 38 represent a nitrogen atom.
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom or a substituent.
  • Ra represents a hydrogen atom or a substituent.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • m and n represent an integer of 1 to 6.
  • X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , X 37 and X 38 each independently represent a nitrogen atom or CRa.
  • One or two of X 31 , X 32 , X 33 and X 34 represent a nitrogen atom.
  • One or two of X 31 , X 32 , X 33 , X 34 , X 35 , X 36 , X 37 and X 38 represent a nitrogen atom.
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom or a substituent.
  • R 3 and Ra represent a hydrogen atom or a substituent.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • m and n represent an integer of 1 to 6.
  • X 31 , X 32 , X 33 , X 34 , X 35 , X 36 and X 38 represented by the general formula (3-6) each independently represent a nitrogen atom or CRa.
  • One or two of X 31 , X 32 , X 33 , X 34 , X 35 , X 36 and X 38 represent a nitrogen atom.
  • One or two of X 35 , X 36 and X 38 represent a nitrogen atom.
  • Ar 0 represents a site connecting an electron-withdrawing group and an electron-donating group or a direct bond.
  • m and n represent an integer of 1 to 6.
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom or a substituent.
  • R 4 and Ra each independently represent a hydrogen atom or a substituent.
  • Rp, Rq, Rr, Rs, Rt and Ru each independently represent a hydrogen atom or a substituent, at least one represents EWG, and at least one represents EDG.
  • x represents an integer of 0 or 1.
  • —Y— and —Z— are each independently represented by a direct bond or —O—, —S— or —N (Rg) —.
  • Rg represents a substituent.
  • Rp, Rq, Rr, Rs, Rt and Ru may be linked to each other to form a bond.
  • Rp 1 , Rq 1 , Rr 1 , Rs 1 , Rt 1 and Ru 1 represented by the general formula (4-2) each independently represent a hydrogen atom or a substituent, and at least one represents EWG, One represents EDG.
  • Rp 1 , Rq 1 , Rr 1 , Rs 1 , Rt 1 and Ru 1 may be linked together to form a bond.
  • Rp 2 , Rq 2 , Rr 2 , Rs 2 , Rt 2 , Ru 2 , Rv 2 and Rw 2 represented by the general formula (4-3) each independently represent a hydrogen atom or a substituent, and at least one One represents EWG and at least one represents EDG.
  • —X— is represented by any of —O—, —S—, —N (Rg) — or —C (Rh) (Ri) —.
  • Rg, Rh and Ri represent a substituent.
  • Rp 2 , Rq 2 , Rr 2 , Rs 2 , Rt 2 , Ru 2 , Rv 2 and Rw 2 may be linked to each other to form a bond.
  • N—R 1 , N—R 2 , N—R 3 , N—R 4 It is also preferable that is represented by an oxygen atom or a sulfur atom.
  • the said fluorescent compound can be synthesize
  • the phosphorescent dopant used in the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and a phosphorescence quantum yield. Is defined as a compound of 0.01 or more at 25 ° C., but a preferable phosphorescence quantum yield is 0.1 or more.
  • the phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition.
  • the phosphorescence dopant used in the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. Just do it.
  • the phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL device. Specific examples of known phosphorescent dopants that can be used in the present invention include compounds described in the following documents. Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/100991, International Publication No.
  • Patent Application Publication No. 2006/0263635 U.S. Patent Application Publication No. 2003/0138657, U.S. Patent Application Publication No. 2003/0152802, U.S. Patent No. 7090928, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics 23, 3745 (2004), Appl. Phys. Lett. 74, 1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/009024, International Publication No. 2006/056418, International Publication No. 2005/019373, International Publication No. 2005/123873, International Publication No.
  • a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, and metal-sulfur bond is preferable.
  • the host compound used in the present invention is a compound mainly responsible for charge injection and transport in the light emitting layer, and its own light emission is not substantially observed in the organic EL device.
  • the host compound preferably has a mass ratio in the layer of 20% or more among the compounds contained in the light emitting layer.
  • a host compound may be used independently or may be used in combination of multiple types. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient.
  • the host compound that is preferably used in the present invention will be described below.
  • the host compound used together with the fluorescent compound in the present invention is not particularly limited, but from the viewpoint of reverse energy transfer, those having an excitation energy larger than the excitation singlet energy of the fluorescent compound according to the present invention are preferable. Further, those having an excitation triplet energy larger than the excitation triplet energy of the fluorescent compound according to the present invention are more preferable.
  • the host compound is responsible for carrier transport and exciton generation in the light emitting layer. Therefore, it can exist stably in all active species states such as cation radical state, anion radical state, and excited state, and does not cause chemical changes such as decomposition and addition reaction. It is preferable not to move at the angstrom level.
  • the light-emitting dopant used in combination exhibits TADF light emission
  • the T 1 energy of the host compound itself is high, and the host compounds are associated with each other.
  • the host compound in prevention of generation of a low T 1 state, that the TADF compound and the host compound does not form a exciplex, such that the host compound does not form a electro-mer by the electric field, 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.
  • host compounds that satisfy these requirements include high ⁇ -energy conjugated skeletons with high T 1 energy, such as carbazole skeleton, azacarbazole skeleton, dibenzofuran skeleton, dibenzothiophene skeleton, or azadibenzofuran skeleton. What has as a partial structure is mentioned preferably.
  • the light-emitting layer contains a carbazole derivative, it is possible to promote appropriate carrier hopping and dispersion of the light-emitting material in the light-emitting layer, and the effect of improving the light-emitting performance of the device and the stability of the thin film can be obtained. Therefore, it is preferable.
  • aryl includes not only an aromatic hydrocarbon ring but also an aromatic heterocyclic ring. More preferably, it is a compound in which a carbazole skeleton and a 14 ⁇ -electron aromatic heterocyclic compound having a molecular structure different from that of the carbazole skeleton are directly bonded, and further a 14 ⁇ -electron aromatic heterocyclic compound is incorporated in the molecule.
  • a carbazole derivative having at least one is preferred.
  • the carbazole derivative is preferably a compound having two or more conjugated structures having 14 ⁇ electrons or more in order to further enhance the effects of the present invention.
  • the 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 preferably has a high T 1
  • the benzene ring (Including polyphenylene skeletons (biphenyl, terphenyl, quarterphenyl, etc.) with multiple benzene rings), fluorene ring, triphenylene ring, carbazole ring, azacarbazole ring, dibenzofuran ring, azadibenzofuran ring, dibenzothiophene ring, dibenzothiophene ring
  • each of the aromatic rings represented by Ar 101 and Ar 102 is preferably a condensed ring having three or more rings. .
  • these rings may further have the above substituent.
  • Specific examples of the aromatic heterocycle condensed with three or more rings include an acridine ring, a benzoquinoline ring, a carbazole ring, a carboline ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a carboline ring, a cyclazine ring, Kindin 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 is a nitrogen atom Phenanthroline ring, dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring
  • 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 general formula (I) only a low Tg small molecular weight of the host compounds represented by not achievable, when 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 the 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 impaired.
  • the compound represented by the general formula (II) is preferably represented by the following general formula (III-1), (III-2) or (III-3).
  • X 101, Ar 102, n102 have the same meanings as X 101, Ar 102, n102 in the general formula (II).
  • R 104 has the same meaning as R 104 in formula (I).
  • 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 the host compound used in the present invention include compounds represented by the general formulas (I), (II), (III-1) to (III-3) and other structures. 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 that can be purified by sublimation or a polymer having a repeating unit.
  • a low molecular weight compound sublimation purification is possible, so that there is an advantage that purification is easy and a high-purity material is easily obtained.
  • the molecular weight is not particularly limited as long as sublimation purification is possible, but the preferred molecular weight is 3000 or less, more preferably 2000 or less.
  • the 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 formula (I), (II) or (III-1) to (III- What has the structure of 3) in a principal chain or a side chain is preferable.
  • the general formula (I), (II) or (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 driving of the element.
  • Tg glass transition temperature
  • Tg is preferably 90 ° C. or higher, more preferably 120 ° C. or higher.
  • the glass transition point (Tg) is a value determined by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).
  • the electron transport layer is made of a material having a function of transporting electrons, and may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • the total thickness of the electron transport layer according to the present invention is not particularly limited, but is usually in the range of 2 nm to 5 ⁇ m, more preferably 2 to 500 nm, and further preferably 5 to 200 nm.
  • the organic EL element when the light generated in the light emitting layer is extracted from the electrode, the light extracted directly from the light emitting layer interferes with the light extracted after being reflected by the electrode from which the light is extracted and the electrode located at the counter electrode. It is known to wake up.
  • the electron mobility of the electron transport layer is preferably 10 ⁇ 5 cm 2 / Vs or more.
  • the material used for the electron transport layer may be any of electron injecting or transporting properties and hole blocking properties, and can be selected from conventionally known compounds. Can be selected and used.
  • nitrogen-containing aromatic heterocyclic derivatives (carbazole derivatives, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring are substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, Triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, azatriphenylene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzthiazole derivatives, etc.), dibenzofuran derivatives, Dibenzothiophene derivatives, silole derivatives, aromatic hydrocarbon ring derivatives (naphthalene derivatives, anthracene derivatives, triphenylene derivatives, etc.) It is.
  • a metal complex having a quinolinol skeleton or a dibenzoquinolinol skeleton as a ligand such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7- Dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc.
  • a metal complex in which the central metal is replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.
  • metal-free or metal phthalocyanine or those in which the terminal thereof is substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material.
  • the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • the electron transport layer may be doped with a doping material as a guest material to form an electron transport layer having a high n property (electron rich).
  • the doping material include n-type dopants such as metal complexes and metal compounds such as metal halides.
  • Specific examples of the electron transport layer having such a structure include, for example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. , 95, 5773 (2004) and the like.
  • More preferable electron transport materials in the present invention include aromatic heterocyclic compounds containing at least one nitrogen atom.
  • aromatic heterocyclic compounds containing at least one nitrogen atom For example, pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, azadibenzofuran derivatives. , Azadibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, benzimidazole derivatives, and the like.
  • the electron transport material may be used alone or in combination of two or more.
  • the hole blocking layer is a layer having a function of an electron transport layer in a broad sense, and is preferably made of a material having a function of transporting electrons while having a small ability to transport holes, and transporting electrons while transporting holes. The probability of recombination of electrons and holes can be improved by blocking.
  • the structure of the electron carrying layer mentioned above can be used as a hole-blocking layer concerning this invention as needed.
  • the hole blocking layer provided in the organic EL device of the present invention is preferably provided adjacent to the cathode side of the light emitting layer.
  • the layer thickness of the hole blocking layer according to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • the material used for a hole-blocking layer the material used for the above-mentioned electron carrying layer is used preferably, and the material used as the above-mentioned host compound is also preferably used for a hole-blocking layer.
  • the electron injection layer (also referred to as “cathode buffer layer”) according to the present invention is a layer provided between the cathode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. It is described in detail in Chapter 2 “Electrode Materials” (pages 123 to 166) of the second edition of “The Forefront of Industrialization (issued by NTT Corporation on November 30, 1998)”.
  • the electron injection layer may be provided as necessary, and may be present between the cathode and the light emitting layer or between the cathode and the electron transport layer as described above.
  • the electron injection layer is preferably a very thin film, and the layer thickness is preferably in the range of 0.1 to 5 nm depending on the material. Moreover, the nonuniform layer (film
  • JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like Specific examples of materials preferably used for the electron injection layer are as follows. , Metals typified by strontium and aluminum, alkali metal compounds typified by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkaline earth metal compounds typified by magnesium fluoride, calcium fluoride, etc., oxidation Examples thereof include metal oxides typified by aluminum, metal complexes typified by 8-hydroxyquinolinate lithium (Liq), and the like. Further, the above-described electron transport material can also be used. Moreover, the material used for said electron injection layer may be used independently, and may be used in combination of multiple types.
  • the hole transport layer contains 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 2 to 500 nm, and further preferably 5 to 200 nm.
  • a material used for the hole transport layer hereinafter referred to as a hole transport material
  • any material that has either a hole injection property or a transport property or an electron barrier property may be used. Any one can be selected and used.
  • porphyrin derivatives for example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives , Indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, and polyvinyl carbazole, polymeric materials or oligomers with aromatic amines introduced into the main chain or side chain, polysilane, conductive And polymer (for example, PEDOT / PSS, aniline copolymer, polyaniline, polythiophene, etc.).
  • PEDOT / PSS aniline copolymer, poly
  • Examples of the triarylamine derivative include a benzidine type typified by ⁇ -NPD, a starburst type typified by MTDATA, and a compound having fluorene or anthracene in the triarylamine linking core part.
  • hexaazatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as hole transport materials.
  • a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, and JP-A-2001-102175. 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 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, and transporting electrons while transporting holes. The probability of recombination of electrons and holes can be improved by blocking.
  • the structure of the positive hole transport layer mentioned above can be used as an electron blocking layer according to the present invention, if necessary.
  • the electron blocking layer provided in the organic EL device of the present invention is preferably provided adjacent to the anode side of the light emitting layer.
  • the thickness of the electron blocking layer according to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • the material used for the electron blocking layer the material used for the above-described hole transport layer is preferably used, and the above-mentioned host compound is also preferably used for the electron blocking layer.
  • the hole injection layer (also referred to as “anode buffer layer”) according to the present invention is a layer provided between the anode and the light emitting layer for the purpose of lowering the driving voltage and improving the light emission luminance. It is described in detail in Volume 2, Chapter 2, “Electrode Materials” (pages 123 to 166) of “The Forefront of Industrialization (issued by NTT Corporation on November 30, 1998)”.
  • the hole injection layer may be provided as necessary, and may be present between the anode and the light emitting layer or between the anode and the hole transport layer as described above.
  • the details of the hole injection layer are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc.
  • materials used for the hole injection layer include: Examples include materials used for the hole transport layer described above. Among them, phthalocyanine derivatives typified by copper phthalocyanine, hexaazatriphenylene derivatives, metal oxides typified by vanadium oxide, amorphous carbon as described in JP-T-2003-519432 and JP-A-2006-135145, etc.
  • the materials used for the hole injection layer described above may be used alone or in combination of two or more.
  • the organic layer in the present invention described above may further contain other additives.
  • the additive include halogen elements such as bromine, iodine and chlorine, halogenated compounds, alkali metals such as Pd, Ca and Na, alkaline earth metals, transition metal compounds, complexes, and salts.
  • the content of the additive can be arbitrarily determined, but is preferably 1000 ppm or less, more preferably 500 ppm or less, and further preferably 50 ppm or less with respect to the total mass% of the contained layer. . However, it is not within this range depending on the purpose of improving the transportability of electrons and holes or the purpose of favoring the exciton energy transfer.
  • a method for forming an organic layer (hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) according to the present invention will be described.
  • the method for forming the organic layer according to the present invention is not particularly limited, and a conventionally known method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used.
  • a conventionally known method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used.
  • the wet method include spin coating method, casting method, ink jet method, printing method, die coating method, blade coating method, roll coating method, spray coating method, curtain coating method, and LB method (Langmuir-Blodgett method).
  • 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.
  • the liquid medium for dissolving or dispersing the organic EL material used in the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
  • ketones such as methyl ethyl ketone and cyclohexanone
  • fatty acid esters such as ethyl acetate
  • halogenated hydrocarbons such as dichlorobenz
  • dispersion method it can disperse
  • the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁇ 6 to 10 ⁇ 2 Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within a range of 50 nm / second, a substrate temperature of ⁇ 50 to 300 ° C., and a layer (film) thickness of 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the organic layer according to the present invention is preferably formed from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. In that case, it is preferable to perform the work in a dry inert gas atmosphere.
  • anode As the anode in the organic EL element, a material having a work function (4 eV or more, preferably 4.5 eV or more) of a metal, an alloy, an electrically conductive compound, or a mixture thereof is preferably used.
  • 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.
  • the anode may be formed by depositing a thin film of these electrode materials by vapor deposition or sputtering, and a pattern having a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 ⁇ m or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. Or when using the substance which can be apply
  • the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
  • cathode As the cathode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, aluminum, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or translucent cathode can be produced by producing a conductive transparent material mentioned in the description of the anode on the cathode after producing the above metal with a thickness of 1 to 20 nm.
  • the support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is transparent. Or opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by J
  • the surface of the resin film may be formed with an inorganic film, an organic film, or a hybrid film of both, and the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992.
  • Relative humidity (90 ⁇ 2)% RH) is preferably 0.01 g / m 2 ⁇ 24 h or less, and 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.
  • any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the method for forming the barrier film is not particularly limited.
  • vacuum deposition sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization
  • a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque support substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.
  • the external extraction quantum efficiency at room temperature (25 ° C.) of light emission of the organic EL device of the present invention is preferably 1% or more, and more preferably 5% or more.
  • external extraction quantum efficiency (%) number of photons emitted to the outside of the organic EL element / number of electrons flowed to the organic EL element ⁇ 100.
  • a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
  • sealing means used for sealing the organic EL element of the present invention include a method of bonding a sealing member, an electrode, and a support substrate with an adhesive.
  • a sealing member it should just be arrange
  • transparency and electrical insulation are not particularly limited. Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • polymer plate examples include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • metal plate examples include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the organic EL element can be thinned.
  • the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 ml / m 2 ⁇ 24 h ⁇ atm or less, and is measured by a method according to JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity 90 ⁇ 2%) is preferably 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ 24 h or less.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable.
  • a desiccant may be dispersed in the adhesive.
  • coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.
  • the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film.
  • the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
  • vacuum deposition sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma
  • a combination method a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase.
  • a vacuum can also be used.
  • a hygroscopic compound can also be enclosed inside. Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
  • metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.
  • perchloric acids eg perchloric acid Barium, magnesium perchlorate, and the like
  • anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • a protective film or a protective plate may be provided outside the sealing film or the sealing film on the side facing the support substrate with the organic layer interposed therebetween.
  • the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate.
  • the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
  • An organic EL element emits light inside a layer having a refractive index higher than that of air (within a refractive index of about 1.6 to 2.1), and is about 15% to 20% of light generated in the light emitting layer. It is generally said that it can only be taken out. This is because light incident on the interface (interface between the transparent substrate and air) at an angle ⁇ greater than the critical angle causes total reflection and cannot be taken out of the device, This is because light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the side surface of the device.
  • a technique for improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the transparent substrate and the air interface (for example, US Pat. No. 4,774,435), A method for improving efficiency by providing light condensing property (for example, Japanese Patent Laid-Open No. 63-134795), a method for forming a reflective surface on the side surface of an element (for example, Japanese Patent Laid-Open No. 1-220394), a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the substrate and the light emitter (for example, Japanese Patent Laid-Open No.
  • these methods can be used in combination with the organic EL device of the present invention.
  • a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
  • by combining these means it is possible to obtain an element having higher luminance or durability.
  • the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally in the range of about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Furthermore, it is preferable that it is 1.35 or less.
  • the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave exuded by evanescent enters the substrate.
  • the method of introducing a diffraction grating into an interface that causes total reflection or in any medium has a feature that the effect of improving the light extraction efficiency is high.
  • This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction, such as first-order diffraction or second-order diffraction.
  • the light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating into any layer or medium (in the transparent substrate or transparent electrode). , Trying to extract light out.
  • the introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
  • the period of the diffraction grating is preferably in the range of about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL element of the present invention can be processed in a specific direction, for example, by combining a so-called condensing sheet with a microlens array structure on the light extraction side of the support substrate (substrate). Condensing light in the front direction with respect to the light emitting surface can increase the luminance in a specific direction.
  • the microlens array quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate. One side is preferably within a range of 10 to 100 ⁇ m.
  • the condensing sheet for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • the shape of the prism sheet for example, the base material may be formed by forming a ⁇ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
  • a light-diffusion plate and a film together with a condensing sheet For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • the organic EL element of the present invention can be used as an electronic device such as a display device, a display, and various light emitting devices.
  • light emitting devices include lighting devices (home lighting, interior lighting), clocks and backlights for liquid crystals, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.
  • the light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 3.16 on page 108 of “New Color Science Handbook” (edited by the Japan Society of Color Science, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total of CS-1000 (manufactured by Konica Minolta Co., Ltd.) is applied to the CIE chromaticity coordinates.
  • the display device including the organic EL element of the present invention may be single color or multicolor, but here, the multicolor display device will be described.
  • a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like.
  • vapor deposition there is no limitation on the method, but a vapor deposition method, an inkjet method, a spin coating method, and a printing method are preferable.
  • the configuration of the organic EL element included in the display device is selected from the above-described configuration examples of the organic EL element as necessary.
  • the manufacturing method of an organic EL element is as having shown in the one aspect
  • a DC voltage When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
  • the alternating current waveform to be applied may be arbitrary.
  • the multicolor display device can be used as a display device, a display, or various light emission sources.
  • a display device or display full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
  • Examples of the display device or display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in 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, a plurality of pixels 3 and the like on a substrate.
  • the main members of the display unit A will be described below.
  • FIG. 3 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
  • the scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated) Not)
  • the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.
  • Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 4 is a schematic diagram showing a pixel circuit.
  • the pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like.
  • a full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.
  • an image data signal is applied from the control unit B to the drain of the switching transistor 11 via the data line 6.
  • a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5
  • the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.
  • the capacitor 13 is charged according to the potential of the image data signal, and the drive transistor 12 is turned on.
  • the drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.
  • the driving of the switching transistor 11 is turned off.
  • the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues.
  • the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
  • the organic EL element 10 emits light by the switching transistor 11 and the drive transistor 12 that are active elements for the organic EL element 10 of each of the plurality of pixels, and the light emission of the organic EL element 10 of each of the plurality of pixels 3. It is carried out.
  • Such a light emitting method is called an active matrix method.
  • the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good.
  • the potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
  • a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.
  • FIG. 5 is a schematic diagram of a passive matrix display device.
  • a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
  • the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal.
  • the pixel 3 has no active element, and the manufacturing cost can be reduced.
  • the organic EL element of the present invention By using the organic EL element of the present invention, a display device with improved luminous efficiency can be obtained.
  • the organic EL element of the present invention can also be used for a lighting device.
  • the organic EL element of the present invention may be used as an organic EL element having a resonator structure.
  • Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.
  • the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection 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 driving method when used as a display device for reproducing a moving image may be either a passive matrix method or an active matrix method. Alternatively, it is possible to produce a full-color display device by using two or more organic EL elements of the present invention having different emission colors.
  • the fluorescent compound used in the present invention can be applied to an organic EL element that emits substantially white light as a lighting device.
  • white light emission can be obtained by simultaneously emitting a plurality of light emission colors and mixing the colors.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of three primary colors of red, green, and blue, or two of the complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.
  • the 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 transport layer, an electron transport layer, or the like, and separately coating with the mask. Since the other layers are common, patterning of a mask or the like is unnecessary, and for example, an electrode film can be formed on one surface by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is improved. According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.
  • FIG. 1 One Embodiment of Lighting Device of the Present Invention.
  • the non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a 300 ⁇ m thick glass substrate is used as a sealing substrate, and an epoxy photocurable adhesive (LUX The track LC0629B) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured, sealed, and illuminated as shown in FIGS.
  • a device can be formed.
  • FIG. 1 An epoxy photocurable adhesive
  • FIG. 6 shows a schematic diagram of the lighting device, and the organic EL element of the present invention (organic EL element 101 in the lighting device) is covered with a glass cover 102 (note that the sealing operation with the glass cover is performed by lighting. This was performed in a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more) without bringing the organic EL element 101 in the apparatus into contact with the air.
  • FIG. 7 is a cross-sectional view of the lighting device, 105 is a cathode, 106 is an organic layer, and 107 is a glass substrate with a transparent electrode.
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • the light emitting material of the present invention has a distance between centers of the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) in the electron density distribution obtained by structural optimization calculation using a semi-empirical molecular orbital calculation method. It contains a fluorescent compound that is in the range of 0.0 to 9.0 mm. As a result, the electron mobility in the organic EL element is improved, and as a result, the emission efficiency is reduced at a high current density in the organic EL element, that is, the effect of improving the roll-off is obtained. An improvement effect is obtained.
  • HOMO highest occupied orbital
  • LUMO lowest unoccupied orbital
  • the longest distance from the molecular center of the lowest unoccupied orbital (LUMO) in the electron density distribution obtained by structural optimization calculation using the semi-empirical molecular orbital calculation method is It is preferable to contain a fluorescent compound that is 0.1 mm or more larger than the van der Waals radius calculated by the semi-empirical molecular orbital calculation method.
  • the fluorescent compound it is preferable to contain a host compound having a structure represented by the general formula (I) or / and the general formula (II). As a result, the effects of further improving the luminous efficiency and improving the lifetime can be obtained.
  • the luminescent material of the present invention can also be used for a luminescent thin film, a display device, and a lighting device.
  • the luminescent thin film of the present invention will be described.
  • the light-emitting thin film of the present invention can be produced in the same manner as the organic layer forming method.
  • the method for forming the light-emitting thin film of the present invention is not particularly limited, and a conventionally known method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used.
  • the wet method include spin coating method, casting method, ink jet method, printing method, die coating method, blade coating method, roll coating method, spray coating method, curtain coating method, and LB method (Langmuir-Blodgett method). From the viewpoint of obtaining a homogeneous thin film easily and high productivity, a method with high roll-to-roll method suitability such as a die coating method, a roll coating method, an ink jet method and a spray coating method is preferable.
  • liquid medium for dissolving or dispersing the light emitting material of 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, mesitylene, and cyclohexyl.
  • Aromatic hydrocarbons such as benzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
  • dispersion method it can disperse
  • different film forming methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is in the range of 50 to 450 ° C., and the degree of vacuum is in the range of 10 ⁇ 6 to 10 ⁇ 2 Pa.
  • the deposition rate is within the range of 0.01 to 50 nm / second
  • the substrate temperature is within the range of ⁇ 50 to 300 ° C.
  • the layer thickness is within the range of 0.1 to 5 ⁇ m, and preferably within the range of 5 to 200 nm. desirable.
  • the light-emitting thin film of the present invention can be used for a display device and a lighting device. As a result, a display device and a lighting device with improved luminous efficiency can be obtained.
  • Table 3 shows the results of calculating the HOMO-LUMO center-to-center distance and VDW distance obtained by structure optimization calculation using the semi-empirical molecular orbital calculation method of the compounds used in the examples and the longest distance from the molecular center to LUMO. Shown in
  • Example 1 ⁇ Production of thin film >> (Method for producing thin film 1-A) A quartz substrate having a size of 50 mm ⁇ 50 mm and a thickness of 0.7 mm was subjected to ultrasonic cleaning with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes. After coating for 30 seconds, it was baked at 120 ° C. for 30 minutes and dried. The thin film was sealed by covering it with a can-shaped glass case in an atmosphere of high-purity nitrogen gas with a purity of 99.999% or higher to produce a thin film 1-A having a thickness of 40 nm.
  • the concentration of the dopant compound 2-4 and the host compound PVK is 100% by mass
  • the concentration of the dopant compound 2-4 is changed to 10%, 20%, 30%, and 40% by mass. A thin film was also produced.
  • Thin films 1-B to 1-E were prepared in the same manner as thin film 1-A except that the dopant compounds were changed as shown in Table 4, and the dopant compound concentrations were 10%, 20%, and 30% by weight. Also, a thin film changed to 40% by mass was prepared.
  • UV-970 (Hitachi, Ltd.) was used for the thin film 1-A to 1-E samples, the UV spectrum was measured, the excitation wavelength was determined, and the PL spectrum of each thin film was measured.
  • an absolute PL quantum yield measuring device C9920-02 manufactured by Hamamatsu Photonics was used.
  • the peak intensity at the emission maximum wavelength (initial maximum wavelength) when the doping concentration of the dopant compound is 5% by mass was set to 1, and the peak intensity at the initial maximum wavelength at each doping concentration was shown in Table 4 as a relative value.
  • Example 2 (Method for producing organic EL element 2-A) A transparent substrate on which ITO (indium tin oxide) is formed as an anode with a thickness of 150 nm on a glass substrate having a thickness of 50 mm ⁇ 50 mm and a thickness of 0.7 mm and patterned, and then this ITO transparent electrode is attached. After ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen gas and UV ozone cleaning for 5 minutes, this transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication.
  • ITO indium tin oxide
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten. After reducing the vacuum to 1 ⁇ 10 ⁇ 4 Pa, energize and heat the deposition crucible containing Ca, deposit on the ITO transparent electrode at a deposition rate of 0.1 nm / second, and form an electron injection layer with a layer thickness of 5 nm Formed. Next, the substrate was moved from the vacuum deposition apparatus to the attached glove box, and a light emitting material having the following composition was applied in a nitrogen atmosphere to form a light emitting layer.
  • Dopant compound 3-1 5 parts by mass Host compound polyvinylcarbazole (PVK) 95 parts by mass Chlorobenzene 20000 parts by mass
  • Organic EL elements 2-B to 2-G were prepared in the same manner as the organic EL element 2-A, except that the compounds used in the organic EL element 2-A were changed to the compounds shown in Table 5.
  • Organic EL device 2-H was produced in the same manner as device 2-A, except that no dopant compound was used.
  • organic EL element 2-H which is a device to which no dopant compound is added
  • the organic mobility in the light emitting layer of the organic EL elements (2-E to 2-G) using the comparative compound is low, and the organic EL element
  • the electron mobility of 2-B and 2-D was almost the same as that of the host compound.
  • organic EL elements 2-A and 2-C showed good electron mobility. This means that when the LUMO distance from the molecular center is 0.1 mm or more larger than the van der Waals radius, that is, when the LUMO exists outside the molecule, electron hopping is good and the electron transport property is improved. Conceivable.
  • Example 3 (Preparation of organic EL device 3-A) A transparent substrate on which ITO (indium tin oxide) is formed as an anode with a thickness of 150 nm on a glass substrate having a thickness of 50 mm ⁇ 50 mm and a thickness of 0.7 mm and patterned, and then this ITO transparent electrode is attached. After ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen gas and UV ozone cleaning for 5 minutes, this transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • the deposition crucible containing ⁇ -NPD was energized and heated, and deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second.
  • a hole injection transport layer was formed.
  • the host compound UGH2 and the dopant compound 2-4 were co-deposited at a deposition rate of 0.1 nm / second so that the volume percentage was 90% and 10%, respectively, to form a light emitting layer having a layer thickness of 35 nm.
  • BCP electron transport material
  • Organic EL elements 3-B to 3-T were produced in the same manner as the organic EL element 3-A, except that the dopant compound 2-4 and the host compound UGH2 were changed as shown in Table 6.
  • Each of the produced organic EL elements was evaluated for roll-off characteristics at room temperature (about 25 ° C.).
  • a graph of luminance vs. external quantum yield obtained when voltage was applied to each element to emit light from 0 to 10,000 cd / A was prepared.
  • the emission luminance was measured using a spectral radiance meter CS-2000 (manufactured by Konica Minolta).
  • the roll-off characteristic R is observed with respect to the emission luminance at which the maximum value of the external quantum yield of each organic EL element was obtained, and the emission luminance at which a decrease in the external quantum yield of 20% was observed. The relative value is shown.
  • Roll-off characteristic R (value of emission luminance at which a decrease in external quantum yield of 20% was observed from the maximum value) / (value of emission luminance at which the maximum value of external quantum yield was obtained) A larger value indicates better roll-off characteristics (less roll-off).
  • the organic EL elements 3-A to 3-L are superior in roll-off characteristics and external quantum yield as compared with the organic EL element of the comparative example. This is presumably because the center-to-center distance between HOMO and LUMO is preferable, and thus it is possible to suppress undesirable interactions such as aggregation between dopant compounds.
  • the organic EL device 3-C of the example since the distance from the molecular center of the fluorescent compound to LUMO is larger than 0.1 mm from the van der Waals radius, the electron transport of the fluorescent compound is As a result, it is considered that the range in which charges can be recombined when the organic EL element is driven is greatly expanded.
  • an organic electroluminescence element capable of improving luminous efficiency can be obtained, and a display device, a display, a home lighting, an interior lighting, a clock or a liquid crystal backlight provided with the organic EL element.
  • Wide light-emitting sources such as signboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light sources of optical sensors, and general household appliances that require display devices can be suitably used.

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Abstract

　Un objet de la présente invention est de produire un élément à électroluminescence organique et un matériau électroluminescent qui permettent un rendement d'émission de lumière amélioré. Un autre objet de l'invention est de produire une pellicule mince électroluminescente contenant le matériau électroluminescent, et un dispositif d'affichage et un dispositif d'éclairage équipé de l'élément à électroluminescence organique, du matériau électroluminescent ou de la pellicule mince électroluminescente. Cet élément à électroluminescence organique comporte, entre une paire d'électrodes, au moins une couche organique incluant une couche organique contenant un composé émetteur de fluorescence, l'élément à électroluminescence organique étant caractérisé en ce que l'espacement de centre à centre de l'orbitale moléculaire occupée la plus haute (HOMO) et l'orbitale moléculaire inoccupée la plus basse (LUMO) dans la distribution de densité d'électrons du composé émetteur de fluorescence, obtenu par des calculs d'optimisation structurelle au moyen d'une méthode de calcul d'orbitale moléculaire semi-empirique, est compris entre 5,0 et 9,0 Å.
PCT/JP2014/072224 2013-08-30 2014-08-26 Élément à électroluminescence organique, matériau électroluminescent, pellicule mince électroluminescente, dispositif d'affichage et dispositif d'éclairage WO2015029964A1 (fr)

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WO2016129687A1 (fr) * 2015-02-13 2016-08-18 出光興産株式会社 Composé, composition, élément organique électroluminescent, et dispositif électronique
WO2016158540A1 (fr) * 2015-03-27 2016-10-06 出光興産株式会社 Élément électroluminescent organique, dispositif électronique et composé
WO2016181846A1 (fr) * 2015-05-08 2016-11-17 コニカミノルタ株式会社 Composé pi-conjugué, matériau électroluminescent organique, matériau électroluminescent, film mince électroluminescent, élément électroluminescent organique, dispositif d'affichage et dispositif d'éclairage
JP2017075121A (ja) * 2015-10-15 2017-04-20 コニカミノルタ株式会社 π共役系化合物、有機エレクトロルミネッセンス素子材料、発光材料、発光性薄膜、有機エレクトロルミネッセンス素子、表示装置及び照明装置
WO2017115068A1 (fr) * 2015-12-29 2017-07-06 University Court Of The University Of St Andrews Composés luminescents
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JP2019509977A (ja) * 2015-12-29 2019-04-11 ユニヴァーシティー コート オブ ザ ユニヴァーシティー オブ セント アンドリューズ 発光性化合物
WO2017115068A1 (fr) * 2015-12-29 2017-07-06 University Court Of The University Of St Andrews Composés luminescents

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