Organometallic complex and organic light emitting element

Abstract

To provide an organometallic complex with both FWHM and FWQM being small in an emission spectrum.SOLUTION: An organometallic complex represented by formula (2a).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an organometallic complex and an organic light-emitting device. [Background technology]

[0002] An organic light-emitting element (hereinafter sometimes referred to as an "organic electroluminescent element" or "organic EL element") is an electronic element having a first electrode, a second electrode, and an organic compound layer disposed between these electrodes. By injecting electrons and holes from this pair of electrodes, excitons of the light-emitting organic compound in the organic compound layer are generated, and when these excitons return to the ground state, the organic light-emitting element emits light. Recent progress in organic light-emitting elements has been remarkable, and their characteristics include low driving voltage, diverse emission wavelengths, fast response, and the ability to make light-emitting devices thinner and lighter. Currently, the use of phosphorescence has been proposed as an attempt to improve the luminous efficiency of organic EL devices. Organic EL devices using phosphorescence are theoretically expected to have luminous efficiency approximately four times higher than fluorescent devices. Therefore, the creation of phosphorescent organometallic complexes has been actively pursued to date. Iridium complexes are representative of phosphorescent organometallic complexes, but their phosphorescent emission spectra generally have a broad full width at half maximum (FWHM). In recent years, attempts have been made to reduce the full width at quarter maximum (FWQM) to achieve higher color purity. Patent Document 1 describes Compound A as a phosphorescent material with a small FWHM, and Patent Document 2 describes Compound B as a light-emitting material with improved current efficiency in a high current density region.

[0003] [ka] [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6991813 [Patent Document 2] Chinese Patent Application Publication No. 103936791 Summary of the Invention [Problem to be solved by the invention]

[0005] Compound A described in Patent Document 1 is a compound with a small FWHM, but there is room for improvement in FWQM to further improve color purity. Compound B described in Patent Document 2 has not been studied for improving FWHM and FWQM, and there is room for improvement in color purity. Although FWHM can be reduced in any phosphorescent material, the structure that can also reduce FWQM is unclear, and there have been challenges in designing a light-emitting material with small FWHM and FWQM. The present invention has been made in view of the above problems, and an object of the present invention is to provide an organometallic complex having small FWHM and FWQM in its emission spectrum. [Means for solving the problem]

[0006] An organometallic complex represented by the following general formula (1): ML m L' n L” l (1) In the general formula (1), M represents a transition metal. L m , L' n , L” l Each represents a different ligand. m is an integer of 1 to 3, n is an integer of 0 to 2, l is an integer of 0 to 2, and m+n+l=2 or 3. ML m is represented by the following general formula (2).

[0007] [ka] In general formula (2), R1 is a hydrogen atom or a deuterium atom. R2 to R 13 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted silyl group, and a cyano group. R 14 are each independently selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted silyl group, and a cyano group. ML' n is represented by the following general formula (3), and ML l is represented by the following general formula (4).

[0008] [ka] In general formulas (3) and (4), R 21 ~R 28 and R 31 ~R 33 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aralkyl group. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an organometallic complex having a small FWHM and FWQM of the emission spectrum. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows the vibrational progression of the emission spectrum due to normal vibrational mode (i). [Figure 2] FIG. 1 is a diagram showing the deviation of normal vibration coordinates between an excited state and a ground state. [Figure 3] 1A is a schematic cross-sectional view showing an example of a pixel of a display device according to one embodiment of the present invention, and FIG. 1B is a schematic cross-sectional view showing an example of a display device using an organic light-emitting element according to one embodiment of the present invention. [Figure 4] 1 is a schematic diagram illustrating an example of a display device according to an embodiment of the present invention. [Figure 5] 1A is a schematic diagram illustrating an example of an imaging device according to an embodiment of the present invention, and FIG. 1B is a schematic diagram illustrating an example of an electronic device according to an embodiment of the present invention. [Figure 6] 1A is a schematic diagram illustrating an example of a display device according to an embodiment of the present invention, and FIG. 1B is a schematic diagram illustrating an example of a foldable display device. [Figure 7] 1A is a schematic diagram showing an example of an illumination device according to an embodiment of the present invention, and FIG. 1B is a schematic diagram showing an example of a moving body having a vehicle lamp according to an embodiment of the present invention. [Figure 8] 1A is a schematic diagram showing an example of a wearable device according to an embodiment of the present invention, and FIG. 1B is a schematic diagram showing another example of a wearable device according to an embodiment of the present invention. [Figure 9] 1A is a schematic diagram illustrating an example of an image forming apparatus according to an embodiment of the present invention, and FIGS. 1B and 1C are schematic diagrams illustrating an example of an exposure light source of the image forming apparatus according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] <Organometallic complexes> The organometallic complex of this embodiment is represented by the following general formula (1). ML m L' n L” l (1)

[0012] <m> In general formula (1), M represents a transition metal. In this specification, the transition metal atom may be divalent, such as Pt, or may be trivalent, and specific examples include Ir, Co, Ru, Os, Rh, and Re, with Ir being preferred.

[0013] <L m , L' n , L” l > In general formula (1), L m , L' n , L” l Each represents a different ligand.

[0014] <m,n,l> In the general formula (1), m is an integer of 1 to 3, n is an integer of 0 to 2, l is an integer of 0 to 2, and m+n+l=2 or 3.

[0015] When m is 1 or 2, it is preferred that n is 0 and l is 1 or 2. l This is because the influence on the emission spectrum is small and the effect of reducing FWHM and FWQM is more easily achieved.

[0016] <ML m > ML m is represented by the following general formula (2): ML m may be the primary ligand.

[0017] [ka]

[0018] [R1] In general formula (2), R1 is a hydrogen atom or a deuterium atom.

[0019] When R1 is a group other than a hydrogen atom or a deuterium atom, R 14 Due to the three-dimensional repulsion with ML m This can cause a twist in the phenanthrene and quinoline parts, which can lead to broadening of the spectral width.

[0020] [R2 to R 13 ] In general formula (2), R to R 13 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted silyl group, and a cyano group.

[0021] R2 to R 13 R may be an alkyl group having from 1 to 10 carbon atoms, an aryl group having from 6 to 18 carbon atoms, a heterocyclic group having from 4 to 12 carbon atoms, an amino group having an aryl group having from 6 to 12 carbon atoms, or a cyano group; may be an alkyl group having from 1 to 7 carbon atoms, an aryl group having from 6 to 12 carbon atoms, a heterocyclic group having from 4 to 12 carbon atoms, or a cyano group; may be an alkyl group having from 1 to 4 carbon atoms, an aryl group having from 6 to 12 carbon atoms, a heterocyclic group having from 4 to 12 carbon atoms, or a cyano group; may be a hydrogen atom, a methyl group, an isopropyl group, a tert-butyl group, a diarylamine group, a phenyl group, a phenyl group having an alkyl group as a substituent, a biphenyl group, or a carbazolyl group; or may be a methyl group or a tert-butyl group. 13 is preferably a hydrogen atom.

[0022] [R 14 ] In general formula (2), R 14 are each independently selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted silyl group, and a cyano group.

[0023] R 14 is preferably an unsubstituted alkyl group or a substituted or unsubstituted aryl group, and more preferably an alkyl group having 1 to 6 carbon atoms.

[0024] <ML’ n ,ML” l > ML' n is represented by the following general formula (3), and ML l is represented by the following general formula (4): n ,ML” l may be an ancillary ligand.

[0025] [ka]

[0026] [R 21 ~R 28 and R 31 ~R 33 ] In general formulas (3) and (4), R 21 ~R 28 and R 31 ~R 33 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aralkyl group.

[0027] In general formula (3), R 21 ~R 28 R may be an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, —CH(C2H5)2, or —C(CH3)(C2H5)2. 21 ~R 28 By making the group a bulky group, the heat resistance, sublimation property, and solubility of the organometallic complex can be improved in some cases.

[0028] In general formula (4), R 31 , R 33 R may be an alkyl having 1 to 8 carbon atoms, or an alkyl having 1 to 6 carbon atoms, or may be a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, —CH(C2H5)2, or —C(CH3)(C2H5)2. 32 R may be an alkyl group having 1 to 4 carbon atoms, and may be a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group. 31 ~R 33 By making R a bulky group, the heat resistance, sublimation property, and solubility of the organometallic complex may be improved. 31 , R 32 , R 33 The combination of R may be an isopropyl group, a hydrogen atom, or an isopropyl group. 31 , R 32 , R 33 The combination of R may be a tert-butyl group, a hydrogen atom, and a tert-butyl group. 31 , R 32 , R 33 The combination of R may be -C(CH3)(C2H5)2, a hydrogen atom, or -C(CH3)(C2H5)2. 31 , R 32 , R 33 The combination of R may be -CH(C2H5)2, a hydrogen atom, or -CH(C2H5)2. 31 , R 32 , R 33 The combination of R may be an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms. 31 and R 33 is an alkyl group having 1 to 6 carbon atoms, and R 32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0029] <Preferred complexes> The organometallic complex of this embodiment is preferably a complex represented by the following general formula (2a).

[0030] [ka]

[0031] Also, R 13 is a hydrogen atom, and R 14 However, a complex in which the alkyl group is an unsubstituted alkyl group, a substituted or unsubstituted aryl group, or more preferably an alkyl group having 1 to 6 carbon atoms is preferred.

[0032] <Description of base> In this specification, halogen atoms include, but are not limited to, fluorine, chlorine, bromine, iodine, etc. Among halogen atoms, fluorine atoms are preferred.

[0033] In this specification, examples of the alkyl group include alkyl groups having from 1 to 10 carbon atoms, more preferably from 1 to 8 carbon atoms, and even more preferably from 1 to 4 carbon atoms. Specific examples include, but are not limited to, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a secondary butyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, and a 2-adamantyl group.

[0034] In this specification, examples of the aryl group include aryl groups having from 6 to 18 carbon atoms, such as a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a phenanthryl group, and a triphenylenyl group.

[0035] In this specification, examples of heterocyclic groups include heterocyclic groups having 3 to 15 carbon atoms. The heterocyclic group may have nitrogen, sulfur, or oxygen as a heteroatom. Specific examples include pyridyl, pyrazyl, pyrimidyl, triazyl, imidazolyl, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, carbazolyl, acridinyl, phenanthrolyl, furanyl, thiophenyl, dibenzofuranyl, and dibenzothiophenyl groups, but are not limited to these.

[0036] In this specification, examples of the amino group include unsubstituted amino groups and amino groups substituted with any of an alkyl group, an aryl group, and an amino group. The alkyl group, the aryl group, and the amino group may have a halogen atom as a substituent. The aryl group and the amino group may have an alkyl group as a substituent. The alkyl groups substituted in the amino group may be bonded to each other to form a ring. Specific examples include, but are not limited to, an N-methylamino group, an N-ethylamino group, an N,N-dimethylamino group, an N,N-diethylamino group, an N-methyl-N-ethylamino group, an N-benzylamino group, an N-methyl-N-benzylamino group, an N,N-dibenzylamino group, an anilino group, an N,N-diphenylamino group, an N,N-dinaphthylamino group, an N,N-difluorenylamino group, an N-phenyl-N-tolylamino group, an N,N-ditolylamino group, an N-methyl-N-phenylamino group, an N,N-dianisolylamino group, an N-mesityl-N-phenylamino group, an N,N-dimesitylamino group, an N-phenyl-N-(4-tert-butylphenyl)amino group, an N-phenyl-N-(4-trifluoromethylphenyl)amino group, and an N-piperidyl group.

[0037] In this specification, examples of alkoxy groups include alkoxy groups having from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms, and even more preferably from 1 to 4 carbon atoms. Specific examples include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, a 2-ethyl-thixyloxy group, and a benzyloxy group.

[0038] In this specification, examples of aryloxy groups and heteroaryloxy groups include, but are not limited to, phenoxy groups and thienyloxy groups.

[0039] In this specification, examples of the silyl group include, but are not limited to, a trimethylsilyl group and a triphenylsilyl group.

[0040] In this specification, examples of aralkyl groups include, but are not limited to, benzyl groups.

[0041] The alkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group, heteroaryloxy group, aralkyl group, and silyl group may have a deuterium atom as a substituent. Examples of alkyl groups having a deuterium atom as a substituent include, but are not limited to, -CD3, (-CD2CH3), and (-CD2CD3).

[0042] The alkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group, heteroaryloxy group, aralkyl group, and silyl group may have a halogen atom as a substituent. Examples of the halogen atom include fluorine, chlorine, and bromine, and may be a fluorine atom. In particular, the alkyl group may have a fluorine atom, thereby becoming a trifluoride methyl group (-CF3) or a pentafluoroethyl group (-CF5).

[0043] The alkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group, heteroaryloxy group, aralkyl group, and silyl group may have an alkyl group as a substituent. The alkyl group may have 1 to 10 carbon atoms. More specifically, the alkyl group may be a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, or a tertiary butyl group.

[0044] The alkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group, heteroaryloxy group, aralkyl group, and silyl group may have an aryl group as a substituent. The aryl group may have 6 to 12 carbon atoms. More specifically, the aryl group may be a phenyl group, a biphenyl group, or a naphthyl group.

[0045] The alkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group, heteroaryloxy group, aralkyl group, and silyl group may have a heterocyclic group as a substituent. The heterocyclic group may have 3 to 9 carbon atoms. The heterocyclic group may have nitrogen, sulfur, or oxygen as a heteroatom. More specifically, the heterocyclic group may be a pyridyl group or a pyrrolyl group.

[0046] The alkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group, heteroaryloxy group, aralkyl group, and silyl group may have an amino group as a substituent. The amino group may have an alkyl group or an aryl group, and the alkyl groups may be bonded to each other to form a ring. Specifically, the amino group may be a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, or a ditolylamino group.

[0047] The alkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group, heteroaryloxy group, aralkyl group, and silyl group may have, as a substituent, an aralkyl group such as a benzyl group, an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group, an aryloxy group such as a phenoxy group, a cyano group, etc. The substituent is not limited to these.

[0048] <Characteristics of organometallic complexes> The organometallic complex according to this embodiment can provide an organic EL material with small FWHM and FWQM in the emission spectrum. The organometallic complex according to this embodiment can provide an organic EL material with small FWHM and FWQM, particularly in the red emission region. Quantum chemical calculations can be utilized to provide such organic EL materials with excellent color purity. Quantum chemical calculations are a computational chemistry approach that predicts molecular properties based on quantum mechanics. The calculation methods used for this prediction are broadly divided into molecular orbital (MO) methods and density functional theory (DFT) methods. Details of the principles are described in "New Quantum Chemistry" by Szabo and Ostlund, University of Tokyo Press, 1991, and "Density Functional Theory of Atoms and Molecules" by Paarl and Young, Springer-Verlag, 1996. Since the luminescence form of the organometallic complex according to this embodiment is phosphorescence, the excited state in the following description refers to the lowest triplet electronic state.

[0049] The emission color of organic electroluminescent materials appears as a spectrum when a molecule transitions from an electronically excited state to its ground state. This emission spectrum exhibits a pattern called vibrational progression, which is caused by a change in molecular structure accompanying the transition from an electronically excited state to the ground state. A molecule consisting of N atoms generally has 3N-6 normal vibrational modes (3N-5 for linear molecules), and changes in molecular structure can be resolved into components of the normal vibrational coordinates corresponding to these normal vibrational modes. When the deviation in the normal vibrational coordinates is small, the energy change in the molecular structure accompanying the deviation can be approximated as a harmonic oscillator. Under this approximation, the vibrational progression of the emission spectrum caused by a certain normal vibrational mode (i) is explained in Figure 1.

[0050] The intensity I of the emission spectrum formulated including all 3N-6 normal vibrational modes has a proportional relationship expressed by the following formula (5). For example, see Yi Jing, Yan, Shaul Mukamel, J. Chem. Phys 85, 5908 (1986).

[0051]

number

[0052] In equation (5), ν 00 is the wave number of the 0-0 transition, and ν em is the wave number of the emission. g(t) is the time domain representation of the inhomogeneous broadening, and is expressed by the following equation (6), and σ t (t) is expressed by the following equation (7).

[0053]

number

[0054] In equation (6), Δν in is the half-width of the spectrum due to inhomogeneous broadening, and varies depending on the environment the molecule is in. Therefore, this value must be obtained experimentally and used as the input value.

[0055]

number

[0056] In equation (7), ω i is the frequency of the normal vibration mode, β=1 / kT (k is Boltzmann's constant, T is temperature), and h is Planck's constant. i is a quantity called the Huang-Rhys factor of normal vibration mode (i) (i = 1 to 3N-6: N is the number of atoms constituting the molecule), and is expressed by the following equation (8).

[0057]

number

[0058] In equation (8), h is Planck's constant and ν i represents the wave number of the normal vibration mode (i). Also, ΔQ i is the deviation of the normal vibrational coordinates between the excited state and the ground state.

[0059] The meaning of this formula is explained in Figure 2. As can be seen from Figure 2 and formula (8), the Hunang-Rhys factor S i is the energy λ of the deviation between the ground state and the excited state of normal vibration mode (i) νib,i is normalized by the energy of its normal vibration mode. Therefore, the Hunang-Rhys factor S i indicates the magnitude of deviation between the molecular structure in the ground state and the excited state in that normal vibration mode (i). A large Huang-Rhys factor in a certain normal vibration mode means that the resulting spectrum broadens significantly. As mentioned earlier, for a molecule consisting of N atoms, there are 3N-6 normal vibration modes (3N-5 for linear molecules), and therefore there are also 3N-6 Huang-Rhys factors, and their magnitudes vary depending on the normal vibration mode.

[0060] Here, to quantify the broadening of the emission spectrum, we use the Huang-Rhys factor defined by equation (8) and define the value PF (Profile Factor) as specified by the following equation (9).

[0061]

number

[0062] In equation (9), the sum area R is the area of ​​a particular normal vibrational mode originating from the molecule, and N basis represents the number of atoms at a particular site on the molecule.

[0063] It is also known that the range of vibrational energy can be classified as follows: CH expansion / contraction: 3000cm -1 End CC ring extension: 1400cm -1 Over 1660cm -1 below CH in-plane bending angle, ring vibration: 1000cm -1 More than 1300cm -1 below CH out-of-plane bending angle: 1000cm -1 below

[0064] The CC ring stretching is the most influential part, but the CH in-plane bending and ring vibration regions also have an effect. Therefore, the normal vibration mode is the 1000cm which includes these regions. -1 More than 1700cm -1 The following regions (mainly CC in-plane expansion / contraction and deformation modes) are considered.

[0065] Therefore, in the case of the light-emitting material of this embodiment, R is 1000 cm -1 More than 1700cm -1 Normal vibration modes in the following regions (mainly CC in-plane stretching and bending modes), N basis is defined as the number of atoms in the basic skeleton of an organic compound, excluding substituents and hydrogen atoms. The PF value indicates the degree of "deviation" between the ground state and excited state of a molecule in the normal vibrational mode of the above-defined region, and is therefore defined as a value equivalent to the numerical amount of the broadening of the emission spectrum caused by this deviation.

[0066] In addition, when calculating the PF value, N basis is the number of atoms in the main skeleton where the transition orbital in the excited state is mainly distributed, and does not take into account atoms of substituents where there is almost no transition orbital. Note that the excited state here means the first singlet excited state S1. The transition orbital means the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

[0067] The validity of this calculation method was verified by comparing the calculated and measured values ​​for organic compounds with and without substituents, using an example in which transition orbitals are hardly distributed among the substituents.

[0068] In this embodiment, the Huang-Rhys factor was calculated using the following method.

[0069] [First calculation step] Geometry optimization calculations were performed to find the most stable structures in the ground and excited states using density functional theory with the functional B3PW91 and basis set LANL2DZ.

[0070] [Second calculation process] Using the most stable structure of the ground state, molecular vibration analysis calculations were performed to determine the vibrational energy of each molecule in the ground state.

[0071] [Third calculation step] Using the most stable structures of the ground and excited states and the vibrational energies of each molecule in the ground state, the Huang-Rhys factors were obtained according to equation (8).

[0072] As software for performing the above calculations, for example, Gaussian 16, Revision C.01, which is electronic structure calculation software, can be used.

[0073] The FWHM and FWQM of an organometallic complex can be determined by calculating the shape of a phosphorescent emission spectrum. For example, a method for calculating the shape of a phosphorescent emission spectrum using the Franck-Condon approximation may be used. In this embodiment, the following method for calculating the shape of a phosphorescent emission spectrum using the Franck-Condon approximation is used.

[0074] [First calculation step] Geometry optimization calculations were performed to find the most stable structures in the ground and excited states using density functional theory with the functional B3PW91 and basis set LANL2DZ.

[0075] [Second calculation process] Using the most stable structure of the ground state and the most stable structure of the excited state, molecular vibration analysis calculations were performed to obtain each molecular vibration wave function and each molecular vibration energy in the ground state and the excited state.

[0076] [Third calculation step] The Franck-Condon factors in the ground state were calculated using each molecular vibrational wave function in the ground state and the lowest molecular vibrational wave function in the excited state.

[0077] [Fourth calculation step] The phosphorescence emission subspectral shape derived from each molecular vibration is calculated by dividing the spectrum by the energy difference between vibrational states, with a width of 800 cm. -1 The phosphorescence subspectral shapes derived from each molecular vibration were superimposed as a Gaussian function whose height is the product of the square of the Franck-Condon factor obtained in the third step and the cube of the energy difference between the vibrational states, thereby obtaining an emission spectral shape with energy as the horizontal axis.

[0078] [Fifth calculation step] By converting the energy into wavelength, the shape of the emission spectrum was obtained with wavelength as the horizontal axis.

[0079] As software for performing the above calculations, for example, Gaussian 16, Revision C.01, which is electronic structure calculation software, can be used.

[0080] Gaussian 16, Revision C.01, MJ Frisch、GW Trucks、HB Schlegel、GE Scuseria、MA Robb, JR Cheeseman, G. Scalmani, V. Barone、GA Petersson、H. Nakatsuji、X. Li, M. Caricato、AV Marenich、J. Bloino、BG Janesko、R. Gomperts、B. Mennucci、HP Hratchian、JV Ortiz、AF Izmaylov、JL Sonnenberg、D. Williams-Young、F. Ding、F. Lipparini、F. Egidi、J. Goings、B. District、A. Petrone、T. Henderson、D. Ranasinghe、VG Zakrzewski、J. Gao, N. Rega、G. Zheng、W. Liang、M. Fairy、M. Ehara、K. Toyota、R. Fukuda、J. Hasegawa、M. Ishida、T. Nakajima、Y. Honda、O. See、H. Thus、T. Vreven、K. Throssell、JA Montgomery, Jr. 、JE Peralta、F. Ogliaro、MJ Bearpark、JJ Heyd、EN Brothers、KN Kudin、VN Staroverov、TA Keith、R. Kobayashi、J. Normand、K. Raghavachari、AP Rendell、JC Burant、SS Iyengar、J. Tomasi, M. Cossi、JM Millam、M. Small、C. Adam、R. Cammi、JW Ochterski、RL Martin、K. Morokuma、O. Farkas、JB Foresman、and DJ Fox、Gaussian、Inc. 、Wallingford CT、2019.

[0081] Here, the emission spectra and PFs of the compounds A to F as comparative compounds and the exemplary compound (1) of this embodiment described later were calculated by quantum chemical calculation. The exemplary compound (1) is represented by the general formula (1), where M is Ir, m=2, n=0, and l=1, and R1 to R 13 is a hydrogen atom, R 14 is a methyl group, and R 31 , R 33 is a methyl group, R 32 is a complex in which L" is a hydrogen atom. l The calculation results for FWHM, FWQM, and PF are shown in Table 1.

[0082] [ka]

[0083] [Table 1]

[0084] As shown in Table 1, Compound A had an FWHM of 50 nm and an FWQM of 77 nm. When compared with Compound B, which had an FWHM of 38 nm and an FWQM of 90 nm, it can be seen that Compound B, which has a phenanthrene skeleton, has a smaller FWHM than Compound A, which has a naphthalene skeleton. However, Compound B has a larger FWQM than Compound A, so there is room for improvement in color purity. Exemplary Compound (1) is a compound having a phenanthrene and quinoline skeleton, and has a smaller FWHM than Compound A and a smaller FWQM than Compound B, making it an emitting material with excellent color purity.

[0085] A decrease in FWQM due to the quinoline skeleton is considered, but when Compound A and Compound C, which have the same naphthalene skeleton, are compared, Compound C, which has a pyridine skeleton, has smaller FWHM and FWQM than Compound A, which has a quinoline skeleton. Therefore, it can be said that the decrease in FWQM due to the quinoline skeleton is an effect exhibited by the combination with the phenanthrene skeleton as in this embodiment.

[0086] Furthermore, a quinoline skeleton is necessary to obtain the effects of the present invention; an isoquinoline skeleton does not provide the effect. Compounds E and F are compounds in which the quinoline skeleton in exemplary compound (1) is replaced with an isoquinoline skeleton. Compound E has larger FWHM and FWQM than exemplary compound (1), indicating that the effect of reducing the emission spectrum width is not achieved. For compound F, the calculations did not converge, and FWHM and FWQM values ​​could not be obtained. This suggests that the molecular structure changes significantly, resulting in a broadening of the emission spectrum width.

[0087] Furthermore, the effect of narrowing the emission spectrum width cannot be obtained even at the bonding position of the phenanthrene skeleton as in Compound D. Therefore, in the phenanthrene skeleton, by orienting the phenanthrene skeleton in a fused ring direction as in Example Compound (1), the electron density of the phenanthrene ring and the accompanying electron transition between carbon and iridium can be controlled, and the MLCT (metal-to-ligand electron transition) property related to emission can be suppressed, thereby making it possible to obtain an organometallic complex with small FWHM and FWQM.

[0088] Furthermore, as described above, the calculation result of PF, which is a quantity that quantifies the spread of the emission spectrum, also shows that the structure of Example Compound (1) has the lowest value, and in particular, in the structure of this embodiment, the PF is 5.00 × 10 -3 or less, it can be predicted that the organometallic complex will have small FWHM and FWQM of the emission spectrum.

[0089] The organometallic complex of this embodiment preferably has a photoluminescence spectrum in solution with a peak top of 610 nm or more and less than 650 nm. The organometallic complex of this embodiment preferably has a calculated FWHM of 50 nm or less and a calculated FWQM of 70 nm or less. The organometallic complex of this embodiment preferably has a calculated FWHM of 50 nm or less and a FWQM of 70 nm or less. -1 More than 1700cm -1 PF in the following area is 5.00×10 -3 It is preferable that:

[0090] <Synthesis method> The organometallic complex according to this embodiment can be synthesized, for example, by the following method: The following method shows the synthesis of exemplary compound (145) as an example.

[0091] [ka]

[0092] <Example> Specific structural formulae of the organometallic complex according to this embodiment are shown below, but the organometallic complex according to this embodiment is not limited to these.

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] The above-mentioned exemplary compounds are examples of organometallic complexes represented by general formula (1). Among the compounds shown, the complex group having three main ligands with a phenanthrene-quinoline skeleton is a stable organometallic complex due to its high molecular symmetry. Furthermore, the complex group having two main ligands with a phenanthrene-quinoline skeleton and one auxiliary ligand has a low molecular weight, which is effective in lowering the deposition temperature. Among these, the organometallic complex containing an acetylacetone (2,4-pentanedione) skeleton as the auxiliary ligand, represented by general formula (4), can be suitably used as a compound that, when appropriately combined with a main ligand containing an appropriate phenanthrene-quinoline skeleton, has a good balance between molecular stability and deposition temperature while maintaining favorable color purity.

[0105] In all of the above organometallic complexes, the main ligand containing the phenanthrene-quinoline skeleton contributes to the emission. As a result, the highly robust cyclic ligand (main ligand) suppresses structural changes within the molecule, and the favorable electron distribution within the ligand (main ligand) contributes to the reduction of the FWHM and FWQM in the emission spectrum.

[0106] Ink composition The ink composition according to this embodiment contains at least one organometallic complex according to this embodiment and a solvent. By using the ink composition according to this embodiment, it is possible to prepare a layer made of an organic compound that constitutes the organic light-emitting device according to this embodiment, particularly a light-emitting layer, by a coating method, and it is possible to easily prepare a large-area device at a relatively low cost. The ink composition according to this embodiment may be a luminous ink composition.

[0107] Examples of solvents that can dissolve the organometallic complex of this embodiment include toluene, xylene, mesitylene, dioxane, methylnaphthalene, tetrahydrofuran, diglyme, 1,2-dichlorobenzene, and 1,2-dichloropropane. These solvents can be used alone or in combination of two or more. Among these, solvents with a moderate evaporation rate, specifically a solvent with a boiling point of about 70°C to 200°C, are preferred, as they facilitate the formation of a thin film with a uniform thickness.

[0108] The ink composition according to this embodiment may also contain other compounds that serve as additives, such as known light-emitting layer hosts or light-emitting assist materials, hole transport materials, light-emitting materials, and electron transport materials, which will be described later.

[0109] The concentration of the organometallic complex of this embodiment in the ink composition of this embodiment is preferably 0.05% by weight or more and 20% by weight or less, and more preferably 0.1% by weight or more and 5% by weight or less, based on the total weight of the composition.

[0110] The ink composition according to this embodiment can be used to form a film by a spin coating method, a bar coating method, a slit coating method, an inkjet method, a nozzle coating method, a casting method, a gravure printing method, etc. The organic light-emitting element according to this embodiment can be used to form an organic light-emitting layer on an electrode formed in a pixel pattern using the ink composition according to this embodiment, thereby constructing a display device such as a display.

[0111] <Organic light-emitting element> The organic light-emitting element of this embodiment has at least a first electrode, a second electrode, and an organic compound layer disposed between these electrodes. One of the first electrode and the second electrode is an anode and the other is a cathode. In the organic light-emitting element of this embodiment, the organic compound layer may be a single layer or a laminate consisting of multiple layers, as long as it has an emitting layer. Here, when the organic compound layer is a laminate consisting of multiple layers, the organic compound layer may have, in addition to the emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole / exciton blocking layer, an electron transport layer, an electron injection layer, etc. Furthermore, the emitting layer may be a single layer or a laminate consisting of multiple layers.

[0112] In the organic light-emitting device of this embodiment, at least one of the organic compound layers contains the organometallic complex of this embodiment. Specifically, the organometallic complex of this embodiment is contained in any of the above-mentioned light-emitting layer, hole injection layer, hole transport layer, electron blocking layer, hole / exciton blocking layer, electron transport layer, electron injection layer, etc. The organometallic complex of this embodiment is preferably contained in the light-emitting layer.

[0113] In the organic light-emitting device of this embodiment, when the organometallic complex according to this embodiment is contained in the light-emitting layer, the light-emitting layer may be a layer consisting solely of the organometallic complex according to this embodiment, or a layer consisting of the organometallic complex according to this embodiment and other compounds. When the light-emitting layer is a layer consisting of the organometallic complex according to this embodiment and other compounds, the organometallic complex according to this embodiment may be used as a host or a guest in the light-emitting layer. It may also be used as an assist material that can be contained in the light-emitting layer. Here, the host is the compound with the largest mass ratio among the compounds constituting the light-emitting layer. The guest is a compound with a mass ratio smaller than that of the host among the compounds constituting the light-emitting layer, and is responsible for the primary emission of light. The assist material is a compound with a mass ratio smaller than that of the host among the compounds constituting the light-emitting layer, and assists the emission of the guest. The assist material is also referred to as a second host. The host material can also be referred to as a first organic compound, and the assist material can also be referred to as a second organic compound. The first organic compound may be a compound with a higher minimum excited singlet energy or a higher minimum excited triplet energy than the organometallic complex according to this embodiment. The lowest excited triplet energy of the second organic compound may be higher than the lowest excited triplet energy of the organometallic complex and lower than the lowest excited triplet energy of the first organic compound.

[0114] When the organometallic complex according to this embodiment is used as a guest in the light-emitting layer, the concentration of the guest is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less, based on the total mass of the light-emitting layer.

[0115] The inventors conducted various studies and found that using the organometallic complex according to this embodiment as a host or guest in the light-emitting layer, particularly as a guest in the light-emitting layer, results in an element exhibiting excellent FWHM and FWQM and extremely high durability. This light-emitting layer may be a single layer or multiple layers, and it is possible to mix the red light emitted by this embodiment with other light-emitting materials by adding other light-emitting materials having different emission colors. "Multiple layers" refers to a state in which the light-emitting layer and another light-emitting layer are stacked. In this case, the emission color of the organic light-emitting element is not limited to red. More specifically, it may be white or a neutral color. In the case of white, the other light-emitting layer emits a color other than red, i.e., blue or green. Furthermore, the film is formed by vapor deposition or coating. Details of this will be explained in detail in the examples below.

[0116] When the organometallic complex according to this embodiment is contained in the light-emitting layer, a first organic compound layer may be provided between the light-emitting layer and the second electrode. The first organic compound layer is preferably a layer having a higher minimum excited triplet energy than the light-emitting layer. Furthermore, a second organic compound layer may be provided between the light-emitting layer and the first electrode. The second organic compound layer is preferably a layer having a higher minimum excited triplet energy than the light-emitting layer.

[0117] The organometallic complex according to this embodiment can be used as a constituent material of an organic compound layer other than the light-emitting layer that constitutes the organic light-emitting device of this embodiment. Specifically, it may be used as a constituent material of an electron transport layer, an electron injection layer, a hole transport layer, a hole injection layer, a hole blocking layer, etc. In this case, the emission color of the organic light-emitting device is not limited to red. More specifically, it may emit white light or an intermediate color.

[0118] <Other compounds> In addition to the organometallic complex according to this embodiment, conventionally known low-molecular-weight and high-molecular-weight hole-injecting or hole-transporting compounds, host compounds, light-emitting compounds, electron-injecting or electron-transporting compounds, etc. may also be used together as needed. Examples of these compounds are listed below.

[0119] As the hole injection and transport material, a material with high hole mobility is preferred so that holes can be easily injected from the anode and the injected holes can be transported to the light-emitting layer. Furthermore, a material with a high glass transition temperature is preferred to suppress deterioration of film quality, such as crystallization, in organic light-emitting devices. Examples of low-molecular-weight and high-molecular-weight materials with hole injection and transport properties include triarylamine derivatives, arylcarbazole derivatives, phenylenediamine derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, poly(vinylcarbazole), poly(thiophene), and other conductive polymers. Furthermore, the above-mentioned hole injection and transport materials are also suitable for use in electron blocking layers. Specific examples of compounds that can be used as hole injection and transport materials are listed below, but the present invention is not limited to these.

[0120] [ka]

[0121] Among these, HT16 to HT18 can reduce the driving voltage when used in a layer in contact with the anode. HT16 is widely used in organic light-emitting devices. HT2, HT3, HT4, HT5, HT6, HT10, and HT12 may be used in an organic compound layer adjacent to HT16. Furthermore, multiple materials may be used in one organic compound layer.

[0122] Examples of light-emitting materials that are primarily involved in light-emitting function include fused ring compounds (e.g., fluorene derivatives, naphthalene derivatives, pyrene derivatives, perylene derivatives, tetracene derivatives, anthracene derivatives, rubrene, etc.), quinacridone derivatives, coumarin derivatives, stilbene derivatives, organoaluminum complexes such as tris(8-quinolinolato)aluminum, iridium complexes, platinum complexes, rhenium complexes, copper complexes, europium complexes, ruthenium complexes, and polymer derivatives such as poly(phenylenevinylene) derivatives, poly(fluorene) derivatives, and poly(phenylene) derivatives. Specific examples of compounds that can be used as light-emitting materials are listed below, but the present invention is not limited to these.

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[0125] When the light-emitting material is a fused polycyclic ring containing a five-membered ring, it is preferable because it has a high ionization potential, is resistant to oxidation, and provides a device with a long and durable life.

[0126] Examples of the light-emitting layer host or light-emitting assist material contained in the light-emitting layer include aromatic hydrocarbon compounds or derivatives thereof, as well as carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, organoaluminum complexes such as tris(8-quinolinolato)aluminum, and organic beryllium complexes. Specific examples of compounds used as the light-emitting layer host or light-emitting assist material contained in the light-emitting layer are shown below, but the present invention is not limited to these.

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[0129] The electron transport material can be arbitrarily selected from those capable of transporting electrons injected from the cathode to the light-emitting layer, and is selected taking into consideration the balance with the hole mobility of the hole transport material. Examples of materials having electron transport properties include oxadiazole derivatives, oxazole derivatives, pyrazine derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, organoaluminum complexes, and fused ring compounds (e.g., fluorene derivatives, naphthalene derivatives, chrysene derivatives, anthracene derivatives, etc.). Furthermore, the above electron transport materials are also suitable for use in hole-blocking layers. Specific examples of compounds used as electron transport materials are shown below, but of course, the present invention is not limited to these.

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[0131] The electron injection material can be selected from those that allow easy electron injection from the cathode, taking into consideration the balance with hole injection properties, etc. Examples of organic compounds include n-type dopants and reducing dopants. Examples include compounds containing alkali metals such as lithium fluoride, lithium complexes such as lithium quinolinol, benzimidazolidene derivatives, imidazolidene derivatives, fulvalene derivatives, and acridine derivatives. They can also be used in combination with the above-mentioned electron transport materials.

[0132] <Configuration of organic light-emitting element> The organic light-emitting element is provided by forming a first electrode, an organic compound layer, and a second electrode on a substrate. An insulating layer may be provided on the substrate. A protective layer, a color filter, a microlens, etc. may be provided on the second electrode. When a color filter is provided, a planarizing layer may be provided between the protective layer. The planarizing layer may be made of acrylic resin, etc. The same applies when a planarizing layer is provided between the color filter and the microlens. Either the first electrode or the second electrode may be an anode, and the other may be a cathode.

[0133] [substrate] Examples of the substrate include quartz, glass, a silicon wafer, a resin, and a metal. Furthermore, the substrate may be provided with a switching element such as a transistor and wiring, and an insulating layer thereon. Any material can be used for the insulating layer, as long as it allows for the formation of a contact hole so that wiring can be formed between the first electrode and the insulating layer, and ensures insulation from wiring that is not connected. For example, resins such as polyimide, silicon oxide, silicon nitride, etc. can be used.

[0134] [electrode] A pair of electrodes can be used. The pair of electrodes may be an anode and a cathode. When an electric field is applied in the direction in which the organic light-emitting element emits light, the electrode with a higher potential is the anode, and the other is the cathode. It can also be said that the electrode that supplies holes to the light-emitting layer is the anode, and the electrode that supplies electrons is the cathode.

[0135] The anode material should have as high a work function as possible. Examples include simple metals such as gold, platinum, silver, copper, nickel, palladium, cobalt, selenium, vanadium, and tungsten, mixtures containing these metals, alloys of these metals, and metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and zinc indium oxide. Conductive polymers such as polyaniline, polypyrrole, and polythiophene can also be used.

[0136] These electrode materials may be used alone or in combination of two or more. The anode may be composed of one layer or multiple layers.

[0137] When used as a reflective electrode, for example, chromium, aluminum, silver, titanium, tungsten, molybdenum, or alloys or laminates thereof can be used. The above materials can also function as a reflective film without functioning as an electrode. When used as a transparent electrode, transparent conductive oxide layers such as indium tin oxide (ITO) and indium zinc oxide can be used, but are not limited to these. Photolithography techniques can be used to form the electrode.

[0138] On the other hand, materials with a low work function are preferred for the cathode. Examples include alkali metals such as lithium, alkaline earth metals such as calcium, and metals such as aluminum, titanium, manganese, silver, lead, and chromium, as well as mixtures containing these metals. Alternatively, alloys combining these metals can be used. For example, magnesium-silver, aluminum-lithium, aluminum-magnesium, silver-copper, and zinc-silver can be used. Metal oxides such as indium tin oxide (ITO) can also be used. These electrode materials can be used alone or in combination. The cathode can have either a single-layer or multi-layer structure. Among these, silver is preferred, and a silver alloy is even more preferred to reduce silver aggregation. The alloy ratio is not critical as long as silver aggregation can be reduced. For example, the silver:other metal ratio can be 1:1, 3:1, or the like.

[0139] The cathode may be a top-emission element using an oxide conductive layer such as ITO, or a bottom-emission element using a reflective electrode such as aluminum (Al), and is not particularly limited. The method for forming the cathode is not particularly limited, but DC and AC sputtering methods are more preferred because they provide good film coverage and make it easier to reduce resistance.

[0140] [Organic compound layer] The organic compound layer may be formed as a single layer or as multiple layers. When multiple layers are included, they may be called hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron transport layer, or electron injection layer depending on their functions. The organic compound layer is mainly composed of organic compounds but may also contain inorganic atoms or inorganic compounds. For example, the organic compound layer may contain copper, lithium, magnesium, aluminum, iridium, platinum, molybdenum, zinc, or the like. The organic compound layer may be disposed between the first electrode and the second electrode, or may be disposed in contact with the first electrode and the second electrode.

[0141] The organic compound layers (hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) constituting the organic light emitting device according to one embodiment of the present invention are formed by the method shown below.

[0142] The organic compound layer constituting the organic light-emitting device according to one embodiment of the present invention can be formed by dry processes such as vacuum deposition, ionization deposition, sputtering, plasma, etc. Alternatively, a wet process can be used in which the compound is dissolved in an appropriate solvent and a layer is formed by a known coating method (e.g., spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, inkjet printing, capillary coating, nozzle coating, LB method, etc.). Among these, vacuum deposition, ionization deposition, inkjet printing, nozzle coating, etc. are suitable for producing a large-area organic light-emitting device.

[0143] Here, when a layer is formed by a vacuum deposition method or a solution coating method, crystallization is unlikely to occur and the layer has excellent stability over time. When a film is formed by a coating method, the film can be formed by combining with an appropriate binder resin.

[0144] Examples of the binder resin include, but are not limited to, polyvinylcarbazole resin, polycarbonate resin, polyester resin, ABS resin, acrylic resin, polyimide resin, phenol resin, epoxy resin, silicone resin, and urea resin.

[0145] These binder resins may be used singly or in combination as homopolymers or copolymers, and may further contain known additives such as plasticizers, antioxidants, and ultraviolet absorbers, if necessary.

[0146] The thickness of each layer in the organic light-emitting device is preferably 1 nm to 10 μm in general, and particularly the thickness of the light-emitting layer of the organic compound layer is preferably 10 nm to 100 nm to obtain effective light-emitting characteristics.

[0147] [Protective layer] A protective layer may be provided on the second electrode. For example, by adhering glass with a moisture absorbent on the second electrode, the infiltration of water and other contaminants into the organic compound layer can be reduced, thereby reducing the occurrence of display defects. In another embodiment, a passivation film such as silicon nitride may be provided on the second electrode to reduce the infiltration of water and other contaminants into the organic compound layer. For example, after forming the second electrode, the second electrode may be transferred to another chamber without breaking the vacuum, and a 2 μm-thick silicon nitride film may be formed by CVD to serve as a protective layer. A protective layer may be provided using atomic layer deposition (ALD) after the CVD film formation. The material of the film formed by ALD is not limited, and may be silicon nitride, silicon oxide, aluminum oxide, or the like. Silicon nitride may be further formed on the film formed by ALD by CVD. The film formed by ALD may have a thickness smaller than that of the film formed by CVD. Specifically, the thickness may be 50% or less, or even 10% or less.

[0148] [Color Filter] A color filter may be provided on the protective layer. For example, a color filter taking into consideration the size of the organic light-emitting element may be provided on a separate substrate and then bonded to the substrate on which the organic light-emitting element is provided, or a color filter may be patterned on the protective layer described above using photolithography technology. The color filter may be made of a polymer.

[0149] [Planarization layer] A planarization layer may be provided between the color filter and the protective layer. The planarization layer is provided for the purpose of reducing the unevenness of the underlying layer. It may also be called a material resin layer without limiting its purpose. The planarization layer may be composed of an organic compound, and may be either a low molecular weight or a high molecular weight, but a high molecular weight is preferred.

[0150] The planarizing layer may be provided above or below the color filter, and may be made of the same or different materials, such as polyvinyl carbazole resin, polycarbonate resin, polyester resin, ABS resin, acrylic resin, polyimide resin, phenol resin, epoxy resin, silicone resin, and urea resin.

[0151] [Microlens] The organic light-emitting element may have an optical component such as a microlens on its light-emitting side. The microlens may be made of acrylic resin, epoxy resin, or the like. The microlens may be intended to increase the amount of light extracted from the organic light-emitting element and control the direction of the extracted light. The microlens may have a hemispherical shape. When the microlens has a hemispherical shape, among the tangents to the hemisphere, there is a tangent that is parallel to the insulating layer, and the point of contact between this tangent and the hemisphere is the vertex of the microlens. The vertex of the microlens can be determined in the same way in any cross-sectional view. In other words, among the tangents to the semicircle of the microlens in the cross-sectional view, there is a tangent that is parallel to the insulating layer, and the point of contact between this tangent and the semicircle is the vertex of the microlens.

[0152] It is also possible to define the midpoint of a microlens. In the cross section of the microlens, a line segment is imagined from the point where an arc shape ends to the point where another arc shape ends, and the midpoint of this line segment can be called the midpoint of the microlens. The cross section for determining the vertex and midpoint may be a cross section perpendicular to the insulating layer.

[0153] [Counter substrate] An opposing substrate may be provided on the planarization layer. The opposing substrate is called an opposing substrate because it is provided at a position corresponding to the aforementioned substrate. The constituent material of the opposing substrate may be the same as that of the aforementioned substrate. When the aforementioned substrate is defined as a first substrate, the opposing substrate may be a second substrate.

[0154] [Pixel circuit] An organic light-emitting device having an organic light-emitting element may have a pixel circuit connected to the organic light-emitting element. The pixel circuit may be an active matrix type that controls the emission of the first light-emitting element and the second light-emitting element independently. The active matrix type circuit may be voltage-programmed or current-programmed. The drive circuit has a pixel circuit for each pixel. The pixel circuit may have a light-emitting element, a transistor that controls the emission brightness of the light-emitting element, a transistor that controls the emission timing, a capacitor that holds the gate voltage of the transistor that controls the emission brightness, and a transistor for connecting to GND without going through the light-emitting element.

[0155] The light-emitting device has a display area and a peripheral area arranged around the display area. The display area has a pixel circuit, and the peripheral area has a display control circuit. The mobility of a transistor constituting the pixel circuit may be smaller than the mobility of a transistor constituting the display control circuit. The slope of the current-voltage characteristics of the transistor constituting the pixel circuit may be smaller than the slope of the current-voltage characteristics of the transistor constituting the display control circuit. The slope of the current-voltage characteristics can be measured by the so-called Vg-Ig characteristics. The transistor constituting the pixel circuit is a transistor connected to a light-emitting element, such as a first light-emitting element.

[0156] [Pixels] An organic light emitting device having an organic light emitting element may have a plurality of pixels, each of which has sub-pixels that emit different colors, for example, RGB colors.

[0157] A pixel emits light from an area called a pixel aperture. This area is the same as the first area. The pixel aperture may be 15 μm or less, or 5 μm or more. More specifically, it may be 11 μm, 9.5 μm, 7.4 μm, 6.4 μm, etc. The distance between subpixels may be 10 μm or less, more specifically, it may be 8 μm, 7.4 μm, or 6.4 μm.

[0158] The pixels may be arranged in a known manner in a plan view. For example, they may be in a stripe arrangement, a delta arrangement, a pentile arrangement, or a Bayer arrangement. The shape of the subpixels in a plan view may be any known shape. For example, they may be rectangular, quadrilaterals such as diamonds, or hexagons. Of course, a shape that is close to a rectangle, rather than an exact shape, is included in the rectangle. The shape of the subpixels and the pixel arrangement may be used in combination.

[0159] <Applications of organic light-emitting devices> The organic light-emitting device according to this embodiment can be used as a component of a display device or a lighting device, and can also be used as an exposure light source for an electrophotographic image forming device, a backlight for a liquid crystal display device, or a light-emitting device having a white light source and a color filter.

[0160] The display device may be an image information processing device having an image input unit that inputs image information from an area CCD, a linear CCD, a memory card, etc., an information processing unit that processes the input information, and displays the input image on a display unit. The display device has a plurality of pixels, at least one of which may have an organic light-emitting element of this embodiment and an active element such as a transistor connected to the organic light-emitting element. In this case, the substrate may be a semiconductor substrate such as silicon, and the transistor may be a MOSFET formed on the substrate. The image display device has an input unit for inputting image information and a display unit for outputting an image, and the display unit has the display device of this embodiment.

[0161] The display unit of the imaging device or inkjet printer may have a touch panel function. The driving method of this touch panel function may be an infrared method, a capacitance method, a resistive film method, or an electromagnetic induction method, and is not particularly limited. The display device may also be used in the display unit of a multifunction printer.

[0162] Next, the display device according to this embodiment will be described with reference to the drawings. Fig. 3 is a cross-sectional view showing an example of a display device having an organic light-emitting element and a transistor connected to the organic light-emitting element. The transistor is an example of an active element. The transistor may be a thin-film transistor (TFT).

[0163] FIG. 3(a) is a cross-sectional schematic diagram of an example of a pixel, which is a component of the display device according to this embodiment. The pixel includes subpixels 10. The subpixels are divided into 10R, 10G, and 10B based on their light emission. The emitted colors may be distinguished by the wavelength of light emitted from the light-emitting layer, or the light emitted from the subpixels may be selectively transmitted or color-converted using a color filter or the like. Each subpixel 10 includes a reflective electrode serving as a first electrode 2 on an interlayer insulating layer 1, an insulating layer 3 covering the edges of the first electrode 2, an organic compound layer 4 covering the first electrode 2 and the insulating layer 3, a transparent electrode serving as a second electrode 5, a protective layer 6, and a color filter 7.

[0164] A transistor and a capacitor element may be disposed below or inside the interlayer insulating layer 1. The transistor and the first electrode 2 may be electrically connected via a contact hole or the like (not shown).

[0165] The insulating layer 3 is also called a bank or a pixel separation film. It covers the edges of the first electrode 2 and is disposed to surround the first electrode 2. The portion where the insulating layer 3 is not disposed is in contact with the organic compound layer 4 and becomes a light-emitting region.

[0166] The organic compound layer 4 includes a hole injection layer 41 , a hole transport layer 42 , a light emitting layer 43 , a hole blocking layer 44 , and an electron transport layer 45 .

[0167] The second electrode 5 may be a transparent electrode, a reflective electrode, or a semi-transparent electrode.

[0168] The protective layer 6 reduces the penetration of moisture into the organic compound layer 4. Although the protective layer 6 is illustrated as being one layer, it may be multiple layers, and each layer may be an inorganic compound layer and an organic compound layer.

[0169] The color filters 7 are divided into 7R, 7G, and 7B depending on their colors. The color filters 7 may be formed on a planarization film (not shown). A resin protective layer (not shown) may be provided on the color filters 7. The color filters 7 may be formed on a protective layer 6. Alternatively, the color filters 7 may be provided on an opposing substrate such as a glass substrate and then bonded thereto.

[0170] The display device 100 in Fig. 3(b) has an organic light-emitting element 26 and a TFT 18, which is an example of a transistor. A substrate 11 made of glass, silicon, or the like is provided with an insulating layer 12 on top of it. An active element such as the TFT 18 is disposed on the insulating layer 12, and a gate electrode 13 of the active element, a gate insulating film 14, and a semiconductor layer 15 are provided. The TFT 18 has a drain electrode 16 and a source electrode 17. An insulating film 19 is provided on top of the TFT 18. An anode 21 constituting the organic light-emitting element 26 and the source electrode 17 are connected via a contact hole 20 provided in the insulating film 19.

[0171] The electrical connection between the electrodes (anode 21, cathode 23) included in the organic light-emitting element 26 and the electrodes (source electrode 17, drain electrode 16) included in the TFT 18 is not limited to the embodiment shown in Fig. 3(b). In other words, it is sufficient that either the anode 21 or the cathode 23 is electrically connected to either the source electrode 17 or the drain electrode 16 of the TFT 18.

[0172] 3(b), the organic compound layer 22 is illustrated as a single layer, but may be a multi-layer organic compound layer 22. A first protective layer 24 and a second protective layer 25 are provided on the cathode 23 to reduce deterioration of the organic light-emitting element 26.

[0173] In the display device 100 of FIG. 3(b), transistors are used as switching elements, but other switching elements such as MIM elements may be used instead.

[0174] The transistors used in the display device 100 of Fig. 3(b) are not limited to thin-film transistors having an active layer on an insulating surface of a substrate, but may also be transistors using a single-crystal silicon wafer. Examples of active layers include single-crystal silicon, amorphous silicon, microcrystalline silicon, and other non-single-crystal silicon, as well as non-single-crystal oxide semiconductors such as indium zinc oxide and indium gallium zinc oxide. Thin-film transistors are also called TFT elements.

[0175] The transistors included in the display device 100 of Fig. 3(b) may be formed within a substrate such as a Si substrate. Here, "formed within a substrate" means that the substrate itself, such as a Si substrate, is processed to form the transistors. In other words, having a transistor within a substrate can be seen as the substrate and the transistor being integrally formed.

[0176] The organic light-emitting element according to this embodiment has its emission brightness controlled by a TFT, which is an example of a switching element. By providing multiple organic light-emitting elements on a surface, an image can be displayed based on the emission brightness of each element. Note that the switching element according to this embodiment is not limited to a TFT, and may be a transistor formed from low-temperature polysilicon or an active matrix driver formed on a substrate such as a Si substrate. "On the substrate" can also be referred to as "inside the substrate." Whether to provide a transistor in the substrate or to use a TFT is determined by the size of the display unit. For example, for a display size of about 0.5 inches, it is preferable to provide the organic light-emitting element on a Si substrate.

[0177] 4 is a schematic diagram illustrating an example of a display device according to this embodiment. The display device 1000 may have a touch panel 1003, a display panel 1005, a frame 1006, a circuit board 1007, and a battery 1008 between an upper cover 1001 and a lower cover 1009. The touch panel 1003 and the display panel 1005 are connected by flexible printed circuits FPCs 1002 and 1004. Transistors are printed on the circuit board 1007. The battery 1008 may not be provided if the display device is not a portable device, and may be provided in a different position even if the display device is a portable device.

[0178] The display device according to this embodiment may have color filters having red, green, and blue colors, which may be arranged in a delta arrangement.

[0179] The display device according to the present embodiment may be used as a display unit of a mobile terminal. In this case, the display device may have both a display function and an operation function. Examples of the mobile terminal include a mobile phone such as a smartphone, a tablet, and a head-mounted display.

[0180] The display device according to this embodiment may be used as a display unit of an imaging device having an optical unit with a plurality of lenses and an imaging element that receives light that has passed through the optical unit. The imaging device may have a display unit that displays information acquired by the imaging element. The display unit may be a display unit exposed to the outside of the imaging device or a display unit disposed within a viewfinder. The imaging device may be a digital camera or a digital video camera.

[0181] 5(a) is a schematic diagram showing an example of an imaging device according to this embodiment. The imaging device 1100 may have a viewfinder 1101, a rear display 1102, an operation unit 1103, and a housing 1104. The viewfinder 1101 may have a display device according to this embodiment. In this case, the display device may display not only an image to be captured, but also environmental information, imaging instructions, and the like. The environmental information may include the intensity of external light, the direction of external light, the speed at which the subject is moving, the possibility that the subject will be blocked by an obstruction, and the like.

[0182] Since the optimum timing for capturing an image is very short, it is better to display information as soon as possible. Therefore, it is preferable to use a display device using the organic light-emitting element of this embodiment. This is because the organic light-emitting element has a fast response speed. Display devices using organic light-emitting elements require high display speed, and these devices can be used more preferably than liquid crystal display devices.

[0183] The imaging device 1100 has an optical section (not shown). The optical section has multiple lenses, which form an image on an imaging element housed in a housing 1104. The focus of the multiple lenses can be adjusted by adjusting their relative positions. This operation can also be performed automatically. The imaging device may also be called a photoelectric conversion device. Instead of sequentially capturing images, the photoelectric conversion device can include an imaging method that detects the difference from the previous image, or a method of cutting out an image from a constantly recorded image, etc.

[0184] FIG. 5(b) is a schematic diagram illustrating an example of an electronic device according to this embodiment. The electronic device 1200 has a display unit 1201, an operation unit 1202, and a housing 1203. The housing 1203 may have a circuit, a printed circuit board having the circuit, a battery, and a communication unit. The operation unit 1202 may be a button or a touch panel type reaction unit. The operation unit 1202 may be a biometric recognition unit that recognizes a fingerprint to perform unlocking or the like. An electronic device having a communication unit can also be called a communication device. The electronic device 1200 may further have a camera function by including a lens and an image sensor. An image captured by the camera function is displayed on the display unit 1201. Examples of the electronic device 1200 include a smartphone and a laptop computer.

[0185] FIG. 6 is a schematic diagram illustrating an example of a display device according to this embodiment. FIG. 6(a) illustrates a display device such as a television monitor or a PC monitor. The display device 1300 has a frame 1301 and a display unit 1302. The display unit 1302 may use a light-emitting element according to this embodiment. The display device 1300 has the frame 1301 and a base 1303 that supports the display unit 1302. The base 1303 is not limited to the form shown in FIG. 6(a). The lower side of the frame 1301 may also serve as the base. The frame 1301 and the display unit 1302 may be curved. The radius of curvature may be 5000 mm or more and 6000 mm or less.

[0186] FIG. 6(b) is a schematic diagram illustrating another example of a display device according to this embodiment. The display device 1310 in FIG. 6(b) is configured to be bendable, and is a so-called foldable display device. The display device 1310 has a first display unit 1311, a second display unit 1312, a housing 1313, and a bending point 1314. The first display unit 1311 and the second display unit 1312 may include light-emitting elements according to this embodiment. The first display unit 1311 and the second display unit 1312 may be a single, seamless display unit. The first display unit 1311 and the second display unit 1312 can be separated by the bending point. The first display unit 1311 and the second display unit 1312 may each display different images, or the first and second display units may display a single image.

[0187] FIG. 7(a) is a schematic diagram illustrating an example of a lighting device according to this embodiment. The lighting device 1400 may include a housing 1401, a light source 1402, a circuit board 1403, an optical filter 1404 that transmits light emitted by the light source 1402, and a light diffusion unit 1405. The light source 1402 may include an organic light-emitting element according to this embodiment. The optical filter 1404 may be a filter that improves the color rendering of the light source. The light diffusion unit 1405 can effectively diffuse light from the light source, such as for illumination, and deliver the light over a wide area. The optical filter 1404 and the light diffusion unit 1405 may be provided on the light emission side of the lighting. If necessary, a cover may be provided on the outermost surface.

[0188] The lighting device is, for example, a device that illuminates a room. The lighting device may emit white, daylight white, or any other color from blue to red. It may have a dimming circuit for dimming them or a color tuning circuit for tuning the emitted color. The lighting device may have the organic light-emitting element of this embodiment and a power supply circuit connected to it. The power supply circuit is a circuit that converts AC voltage to DC voltage. The lighting device may have an inverter circuit. Furthermore, white has a color temperature of 4200K, and daylight white has a color temperature of 5000K. The lighting device may have a color filter.

[0189] The lighting device according to this embodiment may also include a heat dissipation unit, which dissipates heat from within the device to the outside, and may be made of a material such as a metal with a high specific heat capacity or liquid silicon.

[0190] 7(b) is a schematic diagram of an automobile, which is an example of a moving body according to this embodiment. The automobile has tail lamps, which are an example of lighting fixtures. The automobile 1500 has tail lamps 1501, and may be configured to turn on the tail lamps when braking or the like is performed.

[0191] The tail lamp 1501 may include an organic light-emitting element according to this embodiment. The tail lamp 1501 may include a protective member for protecting the organic light-emitting element. The protective member may be made of any material as long as it has a certain degree of strength and is transparent, but is preferably made of polycarbonate or the like. Polycarbonate may be mixed with a furandicarboxylic acid derivative, an acrylonitrile derivative, or the like.

[0192] The automobile 1500 may have a body 1503 and a window 1502 attached thereto. The window 1502 may be a transparent display as long as it is not a window for checking the front and rear of the automobile. The transparent display may have an organic light-emitting element according to this embodiment. In this case, the constituent materials of the electrodes and the like of the organic light-emitting element are made of transparent materials.

[0193] The moving body according to this embodiment may be a ship, an aircraft, a drone, or the like. The moving body may have a body and a lighting device provided on the body. The lighting device may emit light to indicate the position of the body. The lighting device has the organic light-emitting element according to this embodiment.

[0194] An application example of the display device of each of the above-described embodiments will be described with reference to Fig. 8. The display device can be applied to a system that can be attached as a wearable device, such as smart glasses, an HMD, or a smart contact lens. An image capturing and displaying device used in such an application example includes an image capturing device capable of photoelectrically converting visible light and a displaying device capable of emitting visible light.

[0195] Fig. 8(a) is a schematic diagram showing an example of a wearable device according to an embodiment of the present invention. Using Fig. 8(a), glasses 1600 (smart glasses) according to one application example will be described. An imaging device 1602 such as a CMOS sensor or SPAD is provided on the front side of a lens 1601 of the glasses 1600. In addition, a display device according to each of the above-mentioned embodiments is provided on the back side of the lens 1601.

[0196] The glasses 1600 further include a control device 1603. The control device 1603 functions as a power source that supplies power to the image capture device 1602 and the display device. The control device 1603 also controls the operations of the image capture device 1602 and the display device. The lens 1601 is formed with an optical system for focusing light onto the image capture device 1602.

[0197] FIG. 8(b) is a schematic diagram showing another example of a wearable device according to an embodiment of the present invention. Using FIG. 8(b), glasses 1610 (smart glasses) according to one application example will be described. The glasses 1610 have a control device 1612, which is equipped with an imaging device corresponding to the imaging device 1602 in FIG. 8(a) and a display device. A lens 1611 is formed with an optical system for projecting light emitted from the imaging device in the control device 1612 and the display device, and an image is projected onto the lens 1611. The control device 1612 functions as a power source that supplies power to the imaging device and the display device, and also controls the operation of the imaging device and the display device.

[0198] The control device 1612 may include a gaze detection unit that detects the wearer's gaze. The gaze detection may use infrared light. The infrared light emitter emits infrared light toward the eyeball of the user gazing at the display image. An imaging unit with a light-receiving element detects the reflected infrared light from the eyeball, thereby obtaining a captured image of the eyeball. A reduction unit that reduces light from the infrared light emitter to the display unit in a planar view reduces degradation of image quality. The user's gaze toward the displayed image is detected from the captured image of the eyeball obtained by capturing infrared light. Any known method can be applied to gaze detection using the captured image of the eyeball. As an example, a gaze detection method based on a Purkinje image formed by reflection of irradiated light on the cornea can be used. More specifically, gaze detection processing based on the pupil-corneal reflex method is performed. Using the pupil-corneal reflex method, a gaze vector representing the orientation (rotation angle) of the eyeball is calculated based on the image of the pupil and the Purkinje image included in the captured image of the eyeball, thereby detecting the user's gaze.

[0199] A display device according to one embodiment of the present invention may include an imaging device having a light receiving element, and may control the display image of the display device based on user line-of-sight information from the imaging device. Specifically, the display device determines a first field of view area where the user gazes and a second field of view area other than the first field of view area based on the line-of-sight information. The first field of view area and the second field of view area may be determined by a control device of the display device, or may be determined by an external control device and received. In the display area of ​​the display device, the display resolution of the first field of view area may be controlled to be higher than the display resolution of the second field of view area. In other words, the resolution of the second field of view area may be lower than that of the first field of view area.

[0200] The display area includes a first display area and a second display area different from the first display area, and a high-priority area is determined from the first display area and the second display area based on line-of-sight information. The first field of view area and the second field of view area may be determined by a control device of the display device, or may be determined by an external control device and received. The resolution of the high-priority area may be controlled to be higher than the resolution of areas other than the high-priority area. In other words, the resolution of an area with a relatively low priority may be lowered.

[0201] Note that AI may be used to determine the first field of view area and areas with high priority. The AI ​​may be a model configured to estimate the angle of gaze and the distance to an object in the line of sight from an image of the eyeball, using as training data an image of the eyeball and the direction in which the eyeball in the image was actually looking. The AI ​​program may be included in the display device, the imaging device, or an external device. If included in an external device, it is transmitted to the display device via communication.

[0202] When display control is performed based on visual recognition detection, the smart glasses can be preferably applied to smart glasses that further include an imaging device for capturing images of the outside world. The smart glasses can display captured external information in real time.

[0203] 9(a) is a schematic diagram showing an example of an image forming apparatus according to one embodiment of the present invention. The image forming apparatus 40 is an electrophotographic image forming apparatus and includes a photoconductor 27, an exposure light source 28, a charging unit 30, a developing unit 31, a transfer unit 32, a transport roller 33, and a fixing unit 35. Light 29 is irradiated from the exposure light source 28, and an electrostatic latent image is formed on the surface of the photoconductor 27. The exposure light source 28 includes the organic light-emitting element according to this embodiment. The developing unit 31 includes toner and the like. The charging unit 30 charges the photoconductor 27. The transfer unit 32 transfers the developed image to a recording medium 34. The transport roller 33 transports the recording medium 34. The recording medium 34 is, for example, paper. The fixing unit 35 fixes the image formed on the recording medium 34.

[0204] 9(b) and 9(c) are diagrams showing an exposure light source 28 and are schematic diagrams illustrating a state in which multiple light-emitting units 36 are arranged on a long substrate. Arrow 37 indicates the direction parallel to the axis of the photoconductor, the column direction in which the organic light-emitting elements are arranged. This column direction is the same as the axis direction about which the photoconductor 27 rotates. This direction can also be referred to as the long axis direction of the photoconductor 27. FIG. 9(b) shows a configuration in which the light-emitting units 36 are arranged along the long axis direction of the photoconductor 27. FIG. 9(c) shows a configuration different from FIG. 9(b), in which the light-emitting units 36 are arranged alternately in the column direction in the first and second columns. The first and second columns are arranged at different positions in the row direction. In the first column, multiple light-emitting units 36 are arranged at intervals. In the second column, light-emitting units 36 are located at positions corresponding to the intervals between the light-emitting units 36 in the first column. In other words, multiple light-emitting units 36 are also arranged at intervals in the row direction. The arrangement in FIG. 9(c) can also be described as a grid arrangement, a houndstooth arrangement, or a checkerboard pattern.

[0205] As described above, by using the device using the organic light-emitting element according to this embodiment, it is possible to achieve a display with good image quality and stability even over a long period of time. Furthermore, by using the device using the organic light-emitting element according to this embodiment, it is possible to achieve both good visibility outdoors due to highly efficient and bright light output and power-saving display. [Example]

[0206] Examples will be described below, but the present invention is not limited to these examples.

[0207] Example 1 Exemplary compound (145) was synthesized according to the following procedure.

[0208] 1. Synthesis of intermediate 1 [ka]

[0209] Under a nitrogen atmosphere, 5-bromo-2-chlorotoluene (2.00 g, 9.73 mmol), 2-formylphenylboronic acid (1.49 g, 99.3 mmol), bis(triphenylphosphine)palladium dichloride (0.07 g, 0.10 mmol), and sodium carbonate (2.06 g, 194.7 mmol) were dissolved in 16 mL of toluene, 5 mL of ethanol, and 12 mL of water, and the mixture was heated and stirred at 90°C for 3 hours. After the reaction was completed, water was added to extract the organic layer. After concentration, the mixture was purified by silica gel column chromatography (developing solvent: 10% ethyl acetate / toluene), and the resulting liquid was concentrated to obtain 0.88 g of intermediate 1. The structure is 1 The product was identified by H-NMR and GC-MS.

[0210] 2. Synthesis of intermediate 2 [ka]

[0211] Under a nitrogen atmosphere, (methoxymethyl)triphenylphosphine chloride (1.78 g, 5.20 mmol) and potassium tert-butoxide (0.70 g, 6.24 mmol) were dissolved in 8 mL of ultra-dehydrated THF and stirred in an ice bath. Intermediate 1 (0.80 g, 3.50 mmol) was then slowly added and stirred for 3 hours in the ice bath. After the reaction was completed, toluene and water were added and the organic layer was recovered. After concentration, the mixture was purified by silica gel column chromatography (developing solvent: toluene), and the resulting liquid was concentrated to obtain 0.85 g of intermediate 2. The structure is 1 The product was identified by H-NMR and GC-MS.

[0212] 3. Synthesis of intermediate 3 [ka]

[0213] Under a nitrogen atmosphere, intermediate 2 (0.85 g, 3.29 mmol) was dissolved in 20 mL of dichloromethane and stirred in an ice bath. Methanesulfonic acid (1.40 g, 3.86 mmol) was then added dropwise over 10 minutes, and the mixture was stirred in the ice bath for 3 hours. After the reaction was complete, toluene and water were added, and the organic layer was recovered. After concentration, the resulting solid was washed with methanol, yielding 0.70 g of intermediate 3. 1 The product was identified by H-NMR and GC-MS.

[0214] 4. Synthesis of intermediate 4 [ka]

[0215] Under a nitrogen atmosphere, intermediate 3 (0.70 g, 3.07 mmol), pinacolborane (0.88 mL, 6.14 mmol), palladium acetate (6.9 mg, 0.03 mol), SPhos (0.04 g, 0.09 mmol), and triethylamine (1.20 mL, 9.20 mmol) were dissolved in 14 mL of toluene and heated with stirring at 90°C for 4 hours. After the reaction was completed, water was added to extract the organic layer. After concentration, the solution was purified by silica gel column chromatography (developing solvent: 50% heptane / toluene), and the resulting liquid was concentrated to obtain 0.21 g of intermediate 4. The structure is 1 The product was identified by H-NMR and GC-MS.

[0216] 5. Synthesis of Intermediate 5 [ka]

[0217] Under a nitrogen atmosphere, intermediate 4 (0.20 g, 0.63 mmol), chloroisoquinoline (0.11 g, 0.69 mmol), tetrakis(triphenylphosphine)palladium (0.02 g, 0.02 mmol), and sodium carbonate (0.27 g, 2.52 mmol) were dissolved in 3.2 mL of toluene, 1.0 mL of ethanol, and 2.4 mL of water, and the mixture was heated and stirred at 90°C for 1 hour. After the reaction was completed, water was added to extract the organic layer. After concentration, the mixture was purified by silica gel column chromatography (developing solvent: toluene), and the resulting liquid was concentrated to obtain 0.15 g of intermediate 5. The structure is 1 The product was identified by H-NMR and LC-MS.

[0218] 6. Synthesis of intermediate 6 [ka]

[0219] Under a nitrogen atmosphere, intermediate 5 (0.15 g, 0.46 mmol) and iridium chloride trihydrate (0.08 g, 0.22 mmol) were dissolved in 2.5 mL of 2-ethoxyethanol and 1.25 mL of water, and the mixture was heated and stirred at 120°C for 20 hours. After the reaction was completed, the mixture was allowed to cool, and the precipitated solid was collected by filtration to obtain 0.10 g of intermediate 6. The structure is 1 The product was identified by H-NMR and LC-MS.

[0220] 7. Synthesis of exemplary compound (145) [ka]

[0221] Under a nitrogen atmosphere, intermediate 6 (100 mg, 0.06 mmol), 3,7-diethyl-3,7-dimethylnonane-4,6-dione (70 mg, 0.29 mmol), and sodium carbonate (31 mg, 0.29 mmol) were dissolved in 3 mL of 2-ethoxyethanol, and the solution was heated and stirred at 120°C for 6 hours. After the reaction was completed, the mixture was allowed to cool and the precipitated solid was collected by filtration. The obtained solid was purified by silica gel column chromatography (developing solvent: toluene), and the obtained liquid was concentrated to obtain 6.7 mg of exemplary compound (145).

[0222] As a result of NMR measurement, the ratio of peak integral values ​​was in good agreement with the structure, and therefore the obtained compound was confirmed to be exemplary compound (145). The NMR spectrum measurement results are shown below. 1 H-NMR (deuterated chloroform) δ (ppm): 8.66(d,2H),8.56(d,2H),8.24(s,2H),8.12(d,2H),7.51(dd,2H),7.43-7.41(m,2H),7.31-7.03(m,4H),7.1 3(d,2H),7.05(t,2H),6.77-6.74(m,2H),6.47(d,2H),6.37(d,2H),4.70(s,1H),3.36(s,6H),1.22-0.96(m,8H),0.12-0.02(m,12H).

[0223] <Example 2> The exemplary compound (145) obtained in Example 1 was dissolved in toluene at 1.0 × 10 -5 The compound was dissolved at a concentration of 1000 M, and after bubbling with N for 5 minutes, the emission spectrum was measured and its spectral widths, FWHM and FWQM, were calculated. The results are shown in Table 2, with the FWHM and FWQM of Compound A (Comparative Example 1) set at a reference value of 1.00. The peak top of the emission spectrum was 632 nm.

[0224] <Comparative Examples 1 to 4, Examples 3 and 4> Compounds A to D, exemplary compound (1), and exemplary compound (172) were synthesized in the same manner as in Example 1, and their FWHM and FWQM were measured in the same manner as in Example 2. The results are shown in Table 2, with the FWHM and FWQM of compound A (Comparative Example 1) taken as a reference value of 1.00. The peak tops of the emission spectra were 635 nm for compound A, 528 nm for compound B, 547 nm for compound C, 639 nm for compound D, 631 nm for exemplary compound (1), and 633 nm for exemplary compound (172).

[0225] [ka]

[0226] [Table 2]

[0227] As shown in Table 2, the FWHM and FWQM of the organometallic complexes according to this embodiment having a phenanthrene-quinoline skeleton both showed smaller values ​​than the compounds A to D of the comparative examples.

[0228] As described above, the organometallic complex according to this embodiment is a phosphorescent material that exhibits small FWHM and FWQM in the emission spectrum.

[0229] ≪Included components≫ The disclosure of this embodiment includes the following configuration. (Configuration 1) An organometallic complex represented by the following general formula (1): ML m L' n L” l (1) In the general formula (1), M represents a transition metal. L m , L' n , L” l Each represents a different ligand. m is an integer of 1 to 3, n is an integer of 0 to 2, l is an integer of 0 to 2, and m+n+l=2 or 3. ML m is represented by general formula (2). In general formula (2), R1 is a hydrogen atom or a deuterium atom. R2 to R 13 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted silyl group, and a cyano group. R 14 are each independently selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted silyl group, and a cyano group. ML' n is represented by the general formula (3), and ML l is represented by general formula (4). In general formulas (3) and (4), R 21 ~R 28 and R 31 ~R 33 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aralkyl group. (Configuration 2) 2. The organometallic complex according to claim 1, wherein M is Ir. (Configuration 3) 3. The organometallic complex according to claim 1 or 2, which is represented by general formula (2a): (Configuration 4) R 13 is a hydrogen atom, R 14 4. The organometallic complex according to any one of structures 1 to 3, wherein is an unsubstituted alkyl group or a substituted or unsubstituted aryl group.

[0230] (Configuration 5) R 14 5. The organometallic complex according to claim 4, wherein is an alkyl group having 1 to 6 carbon atoms. (Configuration 6) R 31 and R 33 is an alkyl group having 1 to 6 carbon atoms, R 32 6. The organometallic complex according to any one of configurations 1 to 5, wherein is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. (Configuration 7) 7. The organometallic complex according to any one of configurations 1 to 6, wherein the peak top of the photoluminescence spectrum in a solution is 610 nm or more and less than 650 nm. (Configuration 8) 8. The organometallic complex according to any one of configurations 1 to 7, wherein the calculated FWHM is 50 nm or less and the calculated FWQM is 70 nm or less. (Configuration 9) The calculated FWHM is 50 nm or less and the wavenumber is 1000 cm -1 More than 1700cm -1 PF in the following area is 5.00×10 -3 9. The organometallic complex according to any one of configurations 1 to 8, wherein the organometallic complex is:

[0231] (Configuration 10) 10. An ink composition comprising the organometallic complex according to any one of Configurations 1 to 9 and a solvent.

[0232] (Configuration 11) An organic light-emitting device having a first electrode, a second electrode, and an organic compound layer disposed between the first electrode and the second electrode, 10. An organic light-emitting device, wherein at least one of the organic compound layers comprises the organometallic complex according to any one of Configurations 1 to 9. (Configuration 12) the layer containing the organometallic complex is a light-emitting layer, the light-emitting layer further comprises a first organic compound, 12. The organic light-emitting device according to claim 11, wherein the first organic compound has a minimum excited singlet energy and a minimum excited triplet energy higher than those of the organometallic complex. (Configuration 13) the light-emitting layer further comprises a second organic compound different from the first organic compound; The organic light-emitting element according to structure 12, wherein the lowest excited triplet energy of the second organic compound is smaller than the lowest excited triplet energy of the first organic compound and larger than the lowest excited triplet energy of the organometallic complex. (Configuration 14) a first organic compound layer between the light-emitting layer and the second electrode; 14. The organic light-emitting device according to claim 12, wherein the lowest excited triplet energy of the first organic compound layer is higher than the lowest excited triplet energy of the light-emitting layer. (Configuration 15) a second organic compound layer between the light-emitting layer and the first electrode; 15. The organic light-emitting device according to any one of Structures 12 to 14, wherein the lowest excited triplet energy of the second organic compound layer is higher than the lowest excited triplet energy of the light-emitting layer.

[0233] (Configuration 16) 16. A display device comprising a plurality of pixels, at least one of which comprises the organic light-emitting element according to any one of structures 11 to 15 and a transistor connected to the organic light-emitting element. (Configuration 17) an optical unit having a plurality of lenses, an image pickup element that receives light that has passed through the optical unit, and a display unit that displays an image picked up by the image pickup element; 16. An imaging device, wherein the display section comprises the organic light-emitting element according to any one of configurations 11 to 15. (Configuration 18) 16. An electronic device comprising: a display unit having the organic light-emitting element according to any one of configurations 11 to 15; a housing in which the display unit is provided; and a communication unit provided in the housing for communicating with the outside. (Configuration 19) 16. A lighting device comprising: a light source having the organic light-emitting element according to any one of configurations 11 to 15; and a light diffusion section or an optical filter that transmits light emitted by the light source. (Configuration 20) A moving body comprising: a lighting fixture having the organic light-emitting element according to any one of configurations 11 to 15; and a vehicle on which the lighting fixture is provided. (Configuration 21) a photosensitive member and an exposure light source that exposes the photosensitive member; 16. An image forming apparatus, wherein the exposure light source comprises the organic light-emitting element according to any one of the 11 to 15 configurations. [Explanation of symbols]

[0234] 1: interlayer insulating layer, 2: first electrode, 3: insulating layer, 4: organic compound layer, 5: second electrode, 6: protective layer, 7: color filter, 10: subpixel, 11: substrate, 12: insulating layer, 13: gate electrode, 14: gate insulating film, 15: semiconductor layer, 16: drain electrode, 17: source electrode, 18: TFT, 19: insulating film, 20: contact hole, 21: anode, 22: organic compound layer, 23: cathode, 24: first protective layer, 25: second protective layer, 26: organic light-emitting element, 100: display device< / m>

Claims

1. An organometallic complex represented by the following general formula (1): ML m 5 n 5” l ((1) In the general formula (1), M represents a transition metal. L m , L' n , L” l Each represents a different ligand. m is an integer of 1 to 3, n is an integer of 0 to 2, l is an integer of 0 to 2, and m+n+l=2 or 3. ML m is represented by the following general formula (2). 【Chemical 1】 In general formula (2), R 1 is a hydrogen atom or a deuterium atom. R 2 ~R 13 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted silyl group, and a cyano group. R 14 are each independently selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted silyl group, and a cyano group. ML' n is represented by the following general formula (3), and ML" l is represented by the following general formula (4). 【Chemistry 2】 In general formulas (3) and (4), R 21 ~R 28 and R 31 ~R 33 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aralkyl group.

2. 2. The organometallic complex according to claim 1, wherein M is Ir.

3. 3. The organometallic complex according to claim 1, wherein the organometallic complex is represented by the following general formula (2a): 【Chemistry 3】

4. The R 13 is a hydrogen atom, The R 14 3. The organometallic complex according to claim 1, wherein R is an unsubstituted alkyl group or a substituted or unsubstituted aryl group.

5. The R 14 5. The organometallic complex according to claim 4, wherein is an alkyl group having 1 to 6 carbon atoms.

6. The R 31 and R 33 is an alkyl group having 1 to 6 carbon atoms, The R 32 3. The organometallic complex according to claim 1, wherein is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

7. 3. The organometallic complex according to claim 1, wherein the photoluminescence spectrum in a solution has a peak top of 610 nm or more and less than 650 nm.

8. 3. The organometallic complex of claim 1, wherein the calculated FWHM is 50 nm or less and the calculated FWQM is 70 nm or less.

9. The calculated FWHM is 50 nm or less and the wave number is 1000 cm -1 More than 1700cm -1 PF in the following region is 5.00 × 10 -3 3. The organometallic complex according to claim 1, wherein:

10. An ink composition comprising the organometallic complex according to claim 1 or 2 and a solvent.

11. An organic light-emitting device having a first electrode, a second electrode, and an organic compound layer disposed between the first electrode and the second electrode, 3. An organic light-emitting device, wherein at least one of the organic compound layers comprises the organometallic complex according to claim 1.

12. the layer containing the organometallic complex is a light-emitting layer, the light-emitting layer further comprises a first organic compound, The organic light-emitting element according to claim 11, wherein the first organic compound has a minimum excited singlet energy and a minimum excited triplet energy higher than those of the organometallic complex.

13. the light-emitting layer further comprises a second organic compound different from the first organic compound; The organic light-emitting element according to claim 12, wherein the lowest excited triplet energy of the second organic compound is smaller than the lowest excited triplet energy of the first organic compound and is larger than the lowest excited triplet energy of the organometallic complex.

14. a first organic compound layer between the light-emitting layer and the second electrode; The organic light-emitting element according to claim 12, wherein the lowest excited triplet energy of the first organic compound layer is higher than the lowest excited triplet energy of the light-emitting layer.

15. a second organic compound layer between the light-emitting layer and the first electrode; The organic light-emitting element according to claim 12, wherein the lowest excited triplet energy of the second organic compound layer is higher than the lowest excited triplet energy of the light-emitting layer.

16. A display device comprising a plurality of pixels, at least one of the plurality of pixels comprising the organic light-emitting element according to claim 11 and a transistor connected to the organic light-emitting element.

17. an optical unit having a plurality of lenses, an image pickup element that receives light that has passed through the optical unit, and a display unit that displays an image picked up by the image pickup element; An imaging device, wherein the display unit comprises the organic light-emitting element according to claim 11.

18. 12. An electronic device comprising: a display unit having the organic light-emitting element according to claim 11; a housing in which the display unit is provided; and a communication unit provided in the housing for communicating with an external device.

19. 12. A lighting device comprising: a light source having the organic light-emitting element according to claim 11; and a light diffusion section or an optical filter that transmits light emitted by the light source.

20. A moving body comprising: a lighting fixture having the organic light-emitting element according to claim 11; and a vehicle on which the lighting fixture is provided.

21. a photosensitive member and an exposure light source that exposes the photosensitive member; 12. An image forming apparatus, wherein the exposure light source comprises the organic light emitting element according to claim 11.

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