Patent Application
20230100639
The present disclosure relates to an organic light-emitting device and an organic compound.
An organic light-emitting device (hereinafter, also referred to as an “organic electroluminescent device” or “organic EL device”) is an electronic device including a pair of electrodes and an organic compound layer disposed between these electrodes. The injection of electrons and holes from these pairs of electrodes generates excitons in the light-emitting organic compound in the organic compound layer, and when the excitons return to the ground state, the organic light-emitting device emits light.
Recent progress in organic light-emitting devices has been remarkable, and their features include low driving voltage, various emission wavelengths, fast response time, and a contribution to enabling light-emitting apparatuses to be thinner and lighter.
Examples of high-efficiency light-emitting devices include devices containing high-efficiency materials, such as phosphorescent materials. U.S. Patent Application Publication No. 2019/0252619 (hereinafter, referred to as “PTL 1”) describes compounds A-1 and A-2 below.
When compounds A-1 and A-2 described in PTL 1 are used in the light-emitting layers in organic light-emitting devices, there is room for improvement in luminous efficiency.
The present disclosure has been made in light of the foregoing disadvantages and provides an organic light-emitting device having high color purity and superior luminous efficiency and an organic compound. The present disclosure also provides an organic light-emitting device having superior luminous efficiency and driving durability characteristics.
One aspect of the present disclosure is directed to providing an organic light-emitting device including a first electrode, a second electrode, and a light-emitting layer disposed between the first electrode and the second electrode, in which the light-emitting layer contains a first compound and a second compound, the first compound is a compound represented by formula [1] or [2], and the second compound is a hydrocarbon compound,
where in formulae [1] and [2], R1 to R12 and R21 to R32 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted silyl group, and a substituted or unsubstituted amino group,
each m is an integer of 1 or more and 3 or less, and each n is an integer of 0 or more and 2 or less, provided that m+n is 3,
each X is a bidentate ligand, and each partial structure IrX is any of the structures illustrated in formulae [3] to [5],
where in formulae [3] to [5], R41 to R55 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted silyl group, and a substituted or unsubstituted amino group, and adjacent groups of R52 to R55 are optionally taken together to form a ring.
Another aspect of the present disclosure is directed to providing an organic compound represented by formula [1] or [2]:
where in formulae [1] and [2], R1 to R12 and R21 to R32 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted silyl group, and a substituted or unsubstituted amino group, provided that at least one of R1 to R12 and at least one of R21 to R32 are each a tertiary alkyl group having 4 or more carbon atoms,
each m is an integer of 1 or more and 3 or less, and each n is an integer of 0 or more and 2 or less, provided that m+n is 3,
each X is a bidentate ligand, and each partial structure IrX is any of the structures illustrated in formulae [3] to [5]:
where in formulae [3] to [5], R41 to R55 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted silyl group, and a substituted or unsubstituted amino group, and adjacent groups of R52 to R55 are optionally taken together to form a ring.
Further features of the present disclosure will become apparent from the following description of exemplary embodiments with reference to the attached drawings.
An organic light-emitting device according to an embodiment of the present disclosure includes a first electrode, a second electrode, and a light-emitting layer disposed between the first electrode and the second electrode. The light-emitting layer contains a first compound (hereinafter, also referred to as a “dopant material”) and a second compound (hereinafter, also referred to as a “host material”). The dopant material is a compound represented by formula [1] or [2]. The host material is a hydrocarbon compound.
In formulae [1] and [2], R1 to R12 and R21 to R32 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted silyl group, and a substituted or unsubstituted amino group.
Each m is an integer of 1 or more and 3 or less, and each n is an integer of 0 or more and 2 or less, provided that m+n is 3.
Each X is a bidentate ligand. Each partial structure IrX is any of the structures illustrated in formulae [3] to [5].
In formulae [3] to [5], R41 to R55 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted silyl group, and a substituted or unsubstituted amino group. Adjacent groups of R52 to R55 are optionally taken together to form a ring.
The organic light-emitting device according to the present embodiment includes the first electrode, the second electrode, and the light-emitting layer disposed between the first electrode and the second electrode and has the following features.
(1-1) The light-emitting layer contains the dopant material and the host material, the dopant material is a compound represented by formula [1] or [2], and the host material is a hydrocarbon compound. This results in a strong interaction between the dopant material and the host material and easy energy transfer.
(1-2) The effect of (1-1) promotes the hole hopping transport between the dopant material and the host material and thus improves the hole transportability in the light-emitting layer.
These features will be described below.
(1-1) The light-emitting layer contains the dopant material and the host material, the dopant material is a compound represented by formula [1] or [2], and the host material is a hydrocarbon compound. This results in a strong interaction between the dopant material and the host material and results in easy energy transfer.
The compound represented by formula [1] or [2] includes a ligand containing a phenanthrene ring, which is a fused hydrocarbon ring formed of three fused benzene rings. As the host material, a hydrocarbon compound is used, and a fused polycyclic compound can be used. Since the dopant material has a fused-ring structure with low polarity and aromaticity in the ligand, the hydrocarbon compound is selected as the host material. A fused polycyclic group can be introduced. This facilitates the 1C-1C interaction between the host material and the ligand of the dopant material (guest material), thereby facilitating energy transfer from the host material to the guest material.
It is known that in the triplet energy used in phosphorescent devices, energy transfer occurs by the Dexter mechanism. In the Dexter mechanism, energy transfer occurs through contact between molecules. Specifically, the short intermolecular distance between the host material and the dopant material results in efficient energy transfer from the host material to the dopant material. Since the dopant material has the fused-ring structure with low polarity and aromaticity in the ligand, the hydrocarbon compound is selected as the host material. A fused-ring hydrocarbon structure can be introduced. This facilitates the π-π interaction between the host material and the ligand of the dopant material, thereby facilitating energy transfer from the host material to the guest material.
Due to the above-described effect, the triplet excitons generated in the host material are rapidly consumed for light emission, and thus an organic light-emitting device having high luminous efficiency is obtained. It is also possible to reduce the deterioration of the material due to a high-energy triplet excited state caused by further excitation of triplet excitons that are not used for light emission. Thus, the organic light-emitting device has good driving durability characteristics.
(1-2) The effect of (1-1) promotes the hole hopping transport between the dopant material and the host material and thus improves the hole transportability in the light-emitting layer.
The compound represented by formula [1] or [2] has a low highest occupied molecular orbital (HOMO) level due to the effect of containing the phenanthrene ring in the ligand and thus tends to have a lower HOMO level (closer to the vacuum level) than the host material. Holes injected from the hole transport layer are transported by the host material. These holes are transported while being repeatedly trapped and de-trapped between the dopant material and the host material. In this case, similar skeletons can be used for the host material and the dopant material. In this case, the overlap between the fused rings of the host material and the dopant material is strong, thus resulting in efficient hole transfer between the dopant material and the host material. This suppresses a voltage rise at the light-emitting layer and provides an organic light-emitting device operable at a low voltage with good driving durability characteristics.
Moreover, the organic light-emitting device according to the present embodiment can have the following features.
(1-3) The light-emitting layer further contains a third material (hereinafter, also referred to as an “assist material”). The assist material has a lower lowest unoccupied molecular orbital (LUMO) level (farther from the vacuum level) than the host material. This confines both electron and hole carriers in the light-emitting layer, thus providing a highly efficient device.
(1-4) The effect of (1-3) reduces the injection of carriers into an adjacent transport layer through the light-emitting layer to reduce the deterioration of the transport layer, thereby providing a highly durable device.
These features will be described below.
(1-3) The light-emitting layer further contains a third material (hereinafter, also referred to as an “assist material”). The assist material has a lower LUMO level (farther from the vacuum level) than the host material. This confines both electron and hole carriers in the light-emitting layer, thus providing a highly efficient device.
The iridium complex illustrated in formula [1] or [2] promotes the injection of holes into the light-emitting layer. Thus, the efficiency can be increased by injecting electrons and holes into the emission layer in a well-balanced manner. The injection of electrons into the light-emitting layer can be promoted. The host material is a hydrocarbon and thus characterized by a wide band gap. Thus, the host material has a high LUMO level (close to the vacuum level), thus possibly making it difficult for electrons to be injected from an electron transport layer and a hole blocking layer. To facilitate the injection of electrons into the light-emitting layer, an assist material can be further contained. The assist material can have a lower LUMO level than the host material. This improves the injectability of both holes and electrons into the light-emitting layer to maintain a good carrier balance in the light-emitting layer, thus providing a highly efficient light-emitting device.
(1-4) The effect of (1-3) reduces the injection of carriers into an adjacent transport layer through the light-emitting layer to reduce the deterioration of the transport layer, thereby providing a highly durable device.
In the device according to the present embodiment, as described above, the dopant material has the effects of promoting the hole injectability in the light-emitting layer and confining holes in the light-emitting layer by hole trapping. This reduces the injection of holes from the light-emitting layer into the hole-blocking layer and the electron transport layer to reduce the deterioration of the hole-blocking layer and the electron transport layer due to holes.
The assist material having a lower LUMO level than the host material has the effect of promoting the electron injectability and confining electrons in the light-emitting layer by electron trapping. This reduces the injection of electrons from the light-emitting layer to an electron-blocking layer and the hole transport layer to reduce the deterioration of the electron-blocking layer and the hole transport layer by electrons.
The dopant material is a compound represented by formula [1] or [2]. Among the dopant materials, a compound in which at least one selected from the group consisting of R1 to R12 and at least one selected from the group consisting of R21 to R32 are tertiary alkyl groups having 4 or more carbon atoms is an organic compound according to an embodiment of the present disclosure.
R1 to R12, and R21 to R32
In formulae [1] and [2], R1 to R12 and R21 to R32 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted silyl group, and a substituted or unsubstituted amino group.
Non-limiting examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
Non-limiting examples of the alkyl group include a methyl group, an ethyl group, an-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a sec-butyl group, a 3-pentyl group, an octyl group, a cyclohexyl group, a tert-pentyl group, a 3-methylpentan-3-yl group, a 1-adamantyl group, and a 2-adamantyl group. As the alkyl group, an alkyl group having 1 or more and 10 or less carbon atoms can be used.
A non-limiting example of the aralkyl group is a benzyl group.
Non-limiting examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a 2-ethyloctyloxy group, and a benzyloxy group. As the alkoxy group, an alkoxy group having 1 or more and 10 or less carbon atoms can be used.
Non-limiting examples of the aryloxy group include a phenoxy group and a naphthoxy group.
Non-limiting examples of the heteroaryloxy group include a furanyloxy group and a thienyloxy group.
Non-limiting examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a phenanthryl group, a triphenylenyl group, a pyrenyl group, an anthracenyl group, a perylenyl group, a chrysenyl group, and a fluoranthenyl group. As the aryl group, an aryl group having 6 or more and 30 or less carbon atoms can be used.
Non-limiting examples of the heterocyclic group include a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a thienyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, an oxazolyl group, an oxadiazolyl group, a thiazolyl group, a thiadiazolyl group, a carbazolyl group, an acridinyl group, and a phenanthrolinyl group. As the heterocyclic group, a heterocyclic group having 3 or more and 27 or less carbon atoms can be used.
Non-limiting examples of the silyl group include a trimethylsilyl group and a triphenylsilyl group.
Non-limiting examples of the amino group include 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, an N-piperidyl group, a carbazolyl group, and an acridyl group. As the amino group, an amino group having 1 or more and 32 or less carbon atoms can be used.
Non-limiting examples of substituents that may be further contained in the alkyl group, the aralkyl group, the alkoxy group, the aryloxy group, the heteroaryloxy group, the aryl group, the heterocyclic group, the silyl group, and the amino group include a deuterium atom, alkyl groups, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, and a tert-butyl group; aralkyl groups, such as a benzyl group; aryl groups, such as a phenyl group and a biphenyl group; heterocyclic groups, such as a pyridyl group and a pyrrolyl group; amino groups, such as a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, and a ditolylamino group; alkoxy groups, such as a methoxy group, an ethoxy group, and a propoxy group; aryloxy groups, such as a phenoxy group; halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a cyano group; and a thiol group.
At least one of R1 to R12 and at least one of R21 to R32 can each be a tertiary alkyl group having 4 or more carbon atoms. At least one of R9 to R12 and at least one of R29 to R32 can each be a tertiary alkyl group having 4 or more carbon atoms.
Non-limiting examples of the tertiary alkyl group having 4 or more carbon atoms include a tert-butyl group, a tert-pentyl group, a 3-methylpentan-3-yl group, and a 1-adamantyl group. Among these, the tert-butyl group can be used.
The dopant material can be a compound represented by formula [1], where R1 can be a tert-butyl group.
m and n
In formulae [1] and [2], each m is an integer of 1 or more and 3 or less, and each n is an integer of 0 or more and 2 or less, provided that m+n is 3.
Each X is a bidentate ligand. Each partial structure IrX is any of the structures illustrated in formulae [3] to [5].
R41 to R55
In formulae [3] to [5], R41 to R55 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted silyl group, and a substituted or unsubstituted amino group.
Specific examples of the halogen atom, the alkyl group, the aralkyl group, the alkoxy group, the aryloxy group, the heteroaryloxy group, the aryl group, the heterocyclic group, the silyl group, and the amino group that are represented by R41 to R55 include, but are not limited to, the same as those described for R1 to R12 and R21 to R32. As the alkyl group, an alkyl group having 1 or more and 10 or less carbon atoms can be used. As the alkoxy group, an alkoxy group having 1 or more and 10 or less carbon atoms can be used. As the aryl group, an aryl group having 6 or more and 30 or less carbon atoms can be used. As the heterocyclic group, a heterocyclic group having 3 or more and 27 or less carbon atoms can be used. As the amino group, an amino group having 1 or more and 32 or less carbon atoms can be used. Specific examples of substituents that may further be contained in the alkyl group, the aralkyl group, the alkoxy group, the aryloxy group, the heteroaryloxy group, the aryl group, the heterocyclic group, the silyl group, and the amino group include, but are not limited to, the same as those described for R1 to R12 and R21 to R32.
Adjacent groups of R52 to R55 may be taken together to form a ring. The expression “adjacent groups of R52 to R55 are taken together to form a ring” means that a ring formed by taking R52 and R53, R53 and R54, or R54 and R55 together and the benzene ring to which R52 to R55 are attached form a fused ring. The ring formed by taking adjacent groups of R52 to R55 together may be an aromatic ring.
The compound illustrated in formula [1] or [2] has the following features.
(2-1) The ligand contains the phenanthrene ring. This results in an emission wavelength of 520 nm to 540 nm, which is required for a green emission dopant, and can result in an emission wavelength of 520 nm to 535 nm.
(2-2) The ligand contains the phenanthrene ring, thus resulting in high hole transportability.
These features will be described below.
(2-1) The ligand contains the phenanthrene ring. This results in an emission wavelength of 520 nm to 540 nm, which is required for a green emission dopant, and can result in an emission wavelength of 520 nm to 535 nm.
The iridium complex illustrated in formula [1] or [2] has high oscillator strength and high quantum yield of the complex due to the coordination of the phenanthrene ring, which is formed of three fused benzene rings. As presented in Table 1, compounds 1 and 2 in which the ligands each contain a phenanthrene ring have longer emission wavelengths than comparative compound 1, and each have an emission wavelength of 520 nm to 540 nm, which is required for a green emission dopant, and can each have an emission wavelength of 520 nm to 535 nm. Compound 1 is exemplified compound B-1 described below. Compound 2 is exemplified compound H-1 described below.
Regarding the emission wavelength, the peak value of an emission spectrum in a dilute toluene solution was used as the emission wavelength.
(2-2) The ligand contains the phenanthrene ring, thus resulting in high hole transportability.
The iridium complex represented by formula [1] or [2] contains the phenanthrene ring and thus has high hole transportability. This seems to be due to the structure in which the phenanthrene rings of the ligands easily overlap each other and thus hole hopping occurs easily between the ligands.
Moreover, the compound illustrated in formula [1] or [2] can have the following features.
(2-3) At least one selected from the group consisting of R1 to R12 and at least one selected from the group consisting of R21 to R32 are each a tertiary alkyl group having 4 or more carbon atoms, resulting in improved sublimability.
(2-4) At least one of R9 to R12 and at least one of R29 to R32 can each be a tertiary alkyl group having 4 or more carbon atoms.
(2-5) The compound represented by formula [1] has a more optimal emission wavelength as a green light-emitting dopant than the compound represented by formula [2].
These features will be described below.
(2-3) At least one selected from the group consisting of R1 to R12 and at least one selected from the group consisting of R21 to R32 are each a tertiary alkyl group having 4 or more carbon atoms, resulting in improved sublimability.
The iridium complex represented by formula [1] or [2] has the above-described features (2-1) and (2-2) because the ligand contains the phenanthrene ring. Meanwhile, since the iridium complex has such a fused polycyclic moiety, the iridium complex has a high molecular weight and thus may have inferior sublimability. Specifically, the temperature during sublimation purification may be high. The complex may be partially decomposed after sublimation purification. Thus, at least one of R1 to R12 and at least one of R21 to R32 can each be a tertiary alkyl group having 4 or more carbon atoms. This suppresses molecular stacking of the complexes and reduces the sublimation temperature. The alkyl group having 4 or more carbon atoms has a greater exclusion effect between the complexes and is more effective in suppressing molecular stacking. The presence of the tertiary alkyl group can reduce the temperature-induced radical cleavage of a carbon-hydrogen bond located at the benzyl position in the case of a high temperature load.
Table 2 presents the bond dissociation energies of carbon-hydrogen bonds described in ACC. Chem. Res. 36, 255-263 (2003).
A larger value of the bond dissociation energy indicates a stronger bond, and a smaller value thereof indicates a weaker bond. That is, it can be seen that the carbon-hydrogen bond located at the benzyl position is a weak bond. This is because when a hydrogen atom located at the benzyl position is eliminated to generate a radical, the radical is stabilized owing to the π-electron resonance with the neighboring benzene ring. Thus, the carbon-hydrogen bond located at the benzyl position is a weak bond. That is, when a compound has a molecular structure that does not contain a moiety such as a benzyl group, the compound can be one in which the carbon-hydrogen bond is not easily cleaved.
Table 3 presents the sublimation temperatures of materials during sublimation purification. The degree of vacuum during the sublimation purification is in the range of 1×10−3 to 1×10−2 Pa. Compound 5 is exemplified compound A-1 described below. Table 3 indicates that when at least one of R1 to R12 and at least one of R21 to R32 are each a tertiary alkyl group having 4 or more carbon atoms, the compound has a low sublimation temperature.
(2-4) At least one of R9 to R12 and at least one of R29 to R32 can each be a tertiary alkyl group having 4 or more carbon atoms.
The tertiary alkyl group having 4 or more carbon atoms described in (2-3) is a highly electron-donating substituent. In the iridium complex represented by formula [1] or [2], the LUMO is distributed on the side of the pyridine ring attached to the phenanthrene ring of the ligand. Accordingly, when at least one of R9 to R12 and at least one of R29 to R32 are each a tertiary alkyl group having 4 or more carbon atoms, the compound emits shorter-wavelength light with better color purity in terms of green. Table 4 presents the difference in emission wavelength depending on whether Ru in formula [1] is a tert-butyl group. When Rn is a tert-butyl group, the emission wavelength is shortened by 5 nm, and the compound emits light with better color purity in terms of green.
As described in (2-2), the iridium complex represented by formula [1] or [2] contains the phenanthrene ring and thus has high hole transportability. The reason for this is presumably due to the structure in which the phenanthrene rings of the ligands easily overlap each other and thus hole hopping occurs easily between the ligands. Thus, in order not to reduce the overlap between the phenanthrene rings, at least one of R9 to R12 and at least one of R29 to R32 can each be a tertiary alkyl group having 4 or more carbon atoms.
(2-5) The compound represented by formula [1] has a more optimal emission wavelength as a green light-emitting dopant than the compound represented by formula [2].
Comparing Compound 1 with Compound 2 in Table 1, Compound 1 emits shorter-wavelength light with better color purity in terms of green. The compound represented by formula [1] has a shorter emission wavelength because the electron-donating performance of the phenanthrene ring is considered to be lower.
Specific examples of the compound represented by formula [1] or [2], which is a dopant material according to an embodiment of the present disclosure, are illustrated below. However, the present disclosure is not limited thereto.
Exemplified compounds belonging to group A are each a compound that is represented by formula [1] and that contains two ligands each containing a phenanthrene ring. Each of the compounds has two highly planar phenanthrene rings and thus has high hole mobility and a high degree of orientation, thereby improving the light extraction of the light-emitting device.
Exemplified compounds belonging to group B are each a compound that is represented by formula [1] and that contains two ligands each containing a phenanthrene ring, in which each of the phenanthrene ring-containing ligands contains a tertiary alkyl group having 4 or more carbon atoms. Reducing intermolecular stacking can improve the sublimability and reduce concentration quenching in the light-emitting layer.
Exemplified compounds belonging to group C are each a compound that is represented by formula [1] and that contains one ligand containing a phenanthrene ring. Each of the compounds has the highly planar phenanthrene ring and thus has high hole mobility. In addition, each compound has a lower molecular weight and a lower sublimation temperature than compounds belonging to group A.
Exemplified compounds belonging to group D are each a compound that is represented by formula [1] and that contains one ligand containing a phenanthrene ring, in which the phenanthrene ring-containing ligand contains a tertiary alkyl group having 4 or more carbon atoms. The intermolecular stacking can be reduced as compared with the compounds of group C, thus improving the sublimability and reducing concentration quenching in the light-emitting layer.
Exemplified compounds belonging to group E are each a compound that is represented by formula [1] and that contains three ligands each containing a phenanthrene ring. The compound has three highly planar phenanthrene rings and thus has very high hole mobility.
Exemplified compounds belonging to group F are each a compound that is represented by formula [1] and that contains three ligands each containing a phenanthrene ring, in which each of the phenanthrene ring-containing ligands contains a tertiary alkyl group having 4 or more carbon atoms. The intermolecular stacking can be reduced as compared with the compounds of group E, thus improving the sublimability and reducing concentration quenching in the light-emitting layer.
Exemplified compounds belonging to group G are each a compound that is represented by formula [2] and that contains two ligands each containing a phenanthrene ring. The compound has two highly planar phenanthrene rings and thus has high hole mobility and a high degree of orientation, thereby improving the light extraction of the light-emitting device.
Exemplified compounds belonging to group H are each a compound that is represented by formula [2] and that contains two ligands each containing a phenanthrene ring, in which each of the phenanthrene ring-containing ligands contains a tertiary alkyl group having 4 or more carbon atoms. Reducing intermolecular stacking can improve the sublimability and reduce concentration quenching in the light-emitting layer.
Exemplified compounds belonging to group I are each a compound that is represented by formula [2] and that contains one ligand containing a phenanthrene ring. Each of the compounds has the highly planar phenanthrene ring and thus has high hole mobility. In addition, each compound has a lower molecular weight and a lower sublimation temperature than compounds belonging to group G.
Exemplified compounds belonging to group J are each a compound that is represented by formula [2] and that contains one ligand containing a phenanthrene ring, in which the phenanthrene ring-containing ligand contains a tertiary alkyl group having 4 or more carbon atoms. The intermolecular stacking can be reduced as compared with the compounds of group I, thus improving the sublimability and reducing concentration quenching in the light-emitting layer.
Exemplified compounds belonging to group K are each a compound that is represented by formula [2] and that contains three ligands each containing a phenanthrene ring. The compound has three highly planar phenanthrene rings and thus has very high hole mobility.
Exemplified compounds belonging to group L are each a compound that is represented by formula [2] and that contains three ligands each containing a phenanthrene ring, in which each of the phenanthrene ring-containing ligands contains a tertiary alkyl group having 4 or more carbon atoms. The intermolecular stacking can be reduced as compared with the compounds of group K, thus improving the sublimability and reducing concentration quenching in the light-emitting layer.
Among these, the compounds illustrated below can be used.
The host material is a hydrocarbon compound. The host material can have a higher lowest triplet excitation energy (Ti) level than the iridium complex represented by formula [1] or [2], which serves as a dopant material. Specifically, the dopant material according to the present embodiment has a light emission range of 520 nm to 540 nm, and can have a light emission range of 520 nm to 535 nm. Thus, the host material can have a Ti of 2.4 eV or higher. As described above, in order to enhance the interaction with the phenanthrene ring of the ligand of the dopant material, a fused polycyclic compound containing three or more rings can be used.
Moreover, the host material can have the following features.
(3-1) The host material contains, in its skeleton, at least one selected from the group consisting of a triphenylene ring, a chrysene ring, and a fluoranthene ring.
(3-2) The host material contains no SP3 carbon.
These features will be described below.
(3-1) The host material contains, in its skeleton, at least one selected from the group consisting of a triphenylene ring, a chrysene ring, and a fluoranthene ring.
The dopant material according to the present embodiment contains a phenanthrene skeleton in its ligand. The phenanthrene skeleton has a highly planar structure. The dopant material and the host material interact with each other as described in (1-1) and (1-2) above; thus, the host material can also have a highly planar structure. This is because the presence of the highly planar structures allows highly planar moieties to approach each other through interaction. More specifically, the phenanthrene moiety of the dopant material easily approaches the planar moiety of the host material. Thus, the intermolecular distance between the dopant material and the host material should be reduced. The above effect leads to the effect of increasing the efficiency of energy transfer described in (1-1).
Examples of the highly planar structure include structures that are hydrocarbon compounds and contain fused polycycles, such as a triphenylene ring, a chrysene ring, a fluoranthene ring, and a phenanthrene ring. Among these, the triphenylene ring, the chrysene ring, and the fluoranthene ring each have a structure different from the phenanthrene ring of the ligand of the dopant material and interact appropriately with the dopant material. Thus, the dopant material can have a shorter emission wavelength. (3-2) The host material contains no SP3 carbon.
As described in (3-1) above, the dopant material according to the present embodiment is a compound characterized in that the interaction and the luminescence properties are improved by improving the distance between the dopant material and the host material. The host material is a compound that contains no SP3 carbon, so that the distance from the dopant material can be reduced.
While specific examples of the host material are illustrated below, the host material is not limited thereto.
The above-mentioned exemplified compounds are each a compound containing, in its skeleton, at least one selected from the group consisting of a triphenylene ring, a phenanthrene ring, a chrysene ring, and a fluoranthene ring, and containing no SP3 carbon. Thus, these compounds can each have a shorter distance from the dopant material according to the present embodiment, so that each of the compounds serves as the host material that has a strong interaction and that satisfactorily transfers energy to the dopant material. Of these, a compound containing, in its skeleton, any of the triphenylene ring, the chrysene ring, and the fluoranthene ring can be used. A compound containing, in its skeleton, a triphenylene ring has a high degree of planarity and can be particularly used.
The light-emitting layer can further contain an assist material. The assist material can have a lower LUMO level (farther from the vacuum level) than the host material. The assist material can be a compound that partially contains any of the following structures:
where X in the above structure is an oxygen atom, a sulfur atom, or a substituted or unsubstituted carbon atom.
Each of the above structures is useful because it has electron-withdrawing properties and can lower the LUMO level of the assist material. Assist materials containing the above structures as partial structures can be used because they have moderately high electron-withdrawing performance and structures moderate in size and thus are presumably less likely to form exciplexes with the dopant material according to the present embodiment. Examples of the assist materials that seem to be likely to form exciplexes with the dopant material according to the present embodiment include compounds each containing a triazine ring as a partial structure.
The above structures may be unsubstituted or substituted with substituents. The carbon atom represented by X may be unsubstituted or substituted with a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an aryl group, a heterocyclic group, a silyl group, and an amino group.
Non-limiting examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
Non-limiting examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a sec-butyl group, an octyl group, a cyclohexyl group, a 1-adamantyl group, and a 2-adamantyl group.
Non-limiting examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a 2-ethyloctyloxy group, and a benzyloxy group.
Non-limiting examples of the aryloxy group include a phenoxy group and a naphthoxy group.
Non-limiting examples of the heteroaryloxy group include a furanyloxy group and a thienyloxy group.
Non-limiting examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a phenanthryl group, a triphenylenyl group, a pyrenyl group, an anthracenyl group, a perylenyl group, a chrysenyl group, and a fluoranthenyl group.
Non-limiting examples of the heterocyclic group include a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, an oxazolyl group, an oxadiazolyl group, a thiazolyl group, a thiadiazolyl group, a carbazolyl group, an acridinyl group, and a phenanthrolinyl group.
Non-limiting examples of the silyl group include a trimethylsilyl group and a triphenylsilyl group.
Non-limiting examples of the amino group include 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, an N-piperidyl group, a carbazolyl group, and an acridyl group.
The alkyl group, the alkoxy group, the amino group, the aryl group, the heterocyclic group, the aryloxy group, and the silyl group may further contain substituents. Non-limiting examples of the substituents include a deuterium atom; alkyl groups, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, and a tert-butyl group; aralkyl groups, such as a benzyl group; aryl groups, such as a phenyl group and a biphenyl group; heterocyclic groups, such as a pyridyl group and a pyrrolyl group; amino groups, such as a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, and a ditolylamino group: alkoxy groups, such as a methoxy group, an ethoxy group, and a propoxy group; aryloxy groups, such as a phenoxy group; halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and a cyano group.
While specific examples of the assist material are illustrated below, the assist material is not limited thereto.
An organic light-emitting device according to the present embodiment will be described below in detail.
The organic light-emitting device according to the present embodiment includes at least a first electrode, a second electrode, and an organic compound layer disposed between the first electrode and the second electrode. In the organic light-emitting device according to the present embodiment, the organic compound layer may be formed of a single layer or a laminate including multiple layers, as long as it includes a light-emitting layer. When the organic compound layer is formed of a laminate including multiple layers, the organic compound layer may include, in addition to the light-emitting layer, a hole injection layer, a hole transport layer, an electron-blocking layer, a hole/exciton-blocking layer, an electron transport layer, and an electron injection layer, for example. The light-emitting layer may be formed of a single layer or a laminate including multiple layers.
In the organic light-emitting device according to the present embodiment, at least one organic compound layer contains the organic compound according to the present embodiment. Specifically, the organic compound according to the present embodiment is contained in any of the light-emitting layer, the hole injection layer, the hole transport layer, the electron-blocking layer, the hole/exciton-blocking layer, the electron transport layer, the electron injection layer, and so forth described above. The organic compound according to the present embodiment can be contained in the light-emitting layer.
In the organic light-emitting device according to the present embodiment, when the organic compound according to the present embodiment is contained in the light-emitting layer, the light-emitting layer may consist of only the organic compound according to the present embodiment or may be composed of the organic compound according to the present embodiment and another compound. When the light-emitting layer is composed of the organic compound according to the present embodiment and another compound, the organic compound according to the present embodiment may be used as a host or a guest (dopant) in the light-emitting layer. The organic compound may be used as an assist material that can be contained in the light-emitting layer.
The term “host” used here refers to a compound having the highest proportion by mass in compounds contained in the light-emitting layer.
The term “guest” refers to a compound that has a lower proportion by mass than the host in the compounds contained in the light-emitting layer and that is responsible for main light emission. The term “assist material” refers to a compound that has a lower proportion by mass than the host in the compounds contained in the light-emitting layer and that assists the light emission of the guest.
When the organic compound according to the present embodiment is used as a guest in the light-emitting layer, the concentration of the guest is preferably 0.010% or more by mass and 20% or less by mass, more preferably 0.1% or more by mass and 5% or less by mass, based on the entire light-emitting layer.
When the organic compound according to the present embodiment is used as an assist material in the light-emitting layer, the concentration of the assist material is preferably 0.10% or more by mass and 45% or less by mass, more preferably 1% or more by mass and 30% or less by mass, based on the entire light-emitting layer.
The inventors have conducted various studies and have found that when the organic compound according to the present embodiment is used as a host, guest, or assist material of a light-emitting layer, especially as a guest of a light-emitting layer, a device that emits light with high efficiency and high luminance, and that is extremely durable can be provided. The inventors have further found that when the organic compound according to the present embodiment is used as an assist material in the light-emitting layer, a device that emits light with high efficiency and high luminance, and that is extremely durable can be provided. The light-emitting layer may be formed of a single layer or multiple layers, and can contain multiple light-emitting materials. The term “multiple layers” may include a state in which the light-emitting layer and another light-emitting layer are stacked, or a state in which an intermediate layer is stacked between multiple light-emitting layers. Tandem or stacked devices are also acceptable. In these cases, the emission color of the organic light-emitting device is not limited to a single color. More specifically, the emission color may be white or a neutral color.
A film-forming method is vapor deposition or coating. The details thereof will be described in examples below.
The organic compound according to the present embodiment can be used as a component material of an organic compound layer other than the light-emitting layer included in the organic light-emitting device according to the present embodiment. Specifically, the organic compound may be used as a component material of the electron transport layer, the electron injection layer, the hole transport layer, the hole injection layer, the hole-blocking layer, and so forth.
For example, a hole injection compound, a hole transport compound, a compound to be used as a host, a light-emitting compound, an electron injection compound, or an electron transport compound, which is known and has a low or high molecular weight, can be used together with the organic compound according to the present embodiment, as needed. Examples of these compounds will be described below.
As a hole injection-transport material, a material having a high hole mobility can be used so as to facilitate the injection of holes from the anode and to transport the injected holes to the light-emitting layer. To reduce a deterioration in film quality, such as crystallization, in the organic light-emitting device, a material having a high glass transition temperature can be used. Examples of a low- or high-molecular-weight material having the ability to inject and transport holes include triarylamine derivatives, aryl carbazole derivatives, phenylenediamine derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, poly(vinyl carbazole), polythiophene, and other conductive polymers. Moreover, the hole injection-transport material can be used for the electron-blocking layer. Non-limiting specific examples of a compound used as the hole injection-transport material will be described below.
Among the hole transport materials illustrated above, HT16 to HT18 can be used in the layer in contact with the anode to reduce the driving voltage. 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. Multiple materials may be used in a single organic compound layer.
An additional light-emitting dopant may also be used in addition to the light-emitting dopant according to the present embodiment. Examples thereof include fused-ring compounds, such as fluorene derivatives, naphthalene derivatives, pyrene derivatives, perylene derivatives, tetracene derivatives, anthracene derivatives, and rubrene, 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(phenylene vinylene) derivatives, polyfluorene derivatives, and polyphenylene derivatives. Non-limiting specific examples of a compound used as a light-emitting material are described below.
When the light-emitting material is a hydrocarbon compound, the material can reduce a decrease in luminous efficiency due to exciplex formation and a deterioration in color purity due to a change in the emission spectrum of the light-emitting material. The hydrocarbon compound is a compound consisting of only carbon and hydrogen, and BD7, BD8, GD5 to GD9, and RD1 are categorized into the hydrocarbon compounds.
When the light-emitting material is a fused polycyclic compound containing a five-membered ring, the material has a high ionization potential and high resistance to oxidation. This can provide a highly durable device with a long life. BD7, BD8, GD5 to GD9, and RD1 are categorized thereinto.
An additional host material or an additional assist material may be used in addition to the host material or the assist material according to the present embodiment. Examples thereof include aromatic hydrocarbon compounds and derivatives thereof, carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, organoaluminum complexes, such as tris(8-quinolinolato)aluminum, and organoberyllium complexes.
Non-limiting specific examples of such compounds are described below.
When the host material is a hydrocarbon compound, the compound according to the present embodiment can easily trap electrons and holes to contribute to higher efficiency. The term “hydrocarbon compound” used here refers to a compound consisting of only carbon and hydrogen, and EM1 to EM12 and EM16 to EM27 are categorized into hydrocarbon compounds.
The electron transport material can be freely-selected from materials capable of transporting electrons injected from the cathode to the light-emitting layer and is selected in consideration of, for example, the balance with the hole mobility of the hole transport material. Examples of a material having the ability to transport electrons include oxadiazole derivatives, oxazole derivatives, pyrazine derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, organoaluminum complexes, and fused-ring compounds, such as fluorene derivatives, naphthalene derivatives, chrysene derivatives, and anthracene derivatives. The electron transport materials can be used for the hole-blocking layer. Non-limiting specific examples of a compound used as the electron transport material will be described below.
An electron injection material can be freely-selected from materials capable of easily injecting electrons from the cathode and is selected in consideration of, for example, the balance with the hole-injecting properties. As the organic compound, n-type dopants and reducing dopants are also included. Examples thereof include alkali metal-containing compounds, such as lithium fluoride, lithium complexes, such as lithium quinolinolate, benzimidazolidene derivatives, imidazolidene derivatives, fulvalene derivatives, and acridine derivatives.
The organic light-emitting device includes an insulating layer, a first electrode, an organic compound layer, a second electrode over a substrate. A protective layer, a color filter, a microlens may be disposed over the second electrode. In the case of disposing the color filter, a planarization layer may be disposed between the protective layer and the color filter. The planarization layer can be composed of, for example, an acrylic resin. The same applies when a planarization layer is provided between the color filter and the microlens.
Examples of the substrate include silicon wafers, quartz substrates, glass substrates, resin substrates, and metal substrates. The substrate may include a switching element, such as a transistor, a line, and an insulating layer thereon. Any material can be used for the insulating layer as long as a contact hole can be formed in such a manner that a line can be coupled to the first electrode and as long as insulation with a non-connected line can be ensured. For example, a resin, such as polyimide, silicon oxide, or silicon nitride, can be used.
A pair of electrodes can be used. The pair of electrodes may be an anode and a cathode.
In the case where an electric field is applied in the direction in which the organic light-emitting device emits light, an electrode having 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 that the electrode that supplies electrons is the cathode.
As the component material of the anode, a material having a work function as high as possible can be used. Examples of the material that can be used include elemental metals, such as gold, platinum, silver, copper, nickel, palladium, cobalt, selenium, vanadium, and tungsten, mixtures thereof, alloys of combinations thereof, and metal oxides, such as tin oxide, zinc oxide, indium oxide, indium-tin oxide (ITO), and indium-zinc oxide. Additionally, conductive polymers, such as polyaniline, polypyrrole, and polythiophene, may be used.
These electrode materials may be used alone or in combination of two or more. The anode may be formed of a single layer or multiple layers.
When the anode is used as a reflective electrode, for example, chromium, aluminum, silver, titanium, tungsten, molybdenum, an alloy thereof, or a stack thereof may be used. These materials can also be used to act as a reflective film that does not have the role of an electrode. When the anode is used as a transparent electrode, a transparent conductive oxide layer composed of, for example, indium-tin oxide (ITO) or indium-zinc oxide may be used; however, the anode is not limited thereto.
The electrode may be formed by photolithography.
As the component material of the cathode, a material having a lower work function can be used. Examples thereof include elemental metals such as alkali metals, e.g., lithium, alkaline-earth metals, e.g., calcium, aluminum, titanium, manganese, silver, lead, and chromium, and mixtures thereof. Alloys of combinations of these elemental metals can also 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 may be used alone or in combination of two or more. The cathode may have a single-layer structure or a multilayer structure. In particular, silver can be used. To reduce the aggregation of silver, a silver alloy can be used. Any alloy ratio may be used as long as the aggregation of silver can be reduced. The ratio of silver to another metal may be, for example, 1:1 or 3:1.
Atop emission device may be provided using the cathode formed of a conductive oxide layer composed of, for example, ITO. A bottom emission device may be provided using the cathode formed of a reflective electrode composed of, for example, aluminum (Al). Any type of cathode may be used. Any method for forming the cathode may be employed. For example, a direct-current or alternating-current sputtering technique can be employed because good film coverage is obtained and thus the resistance is easily reduced.
The organic compound layer may be formed of a single layer or multiple layers. When multiple layers are present, they may be referred to as a hole injection layer, a hole transport layer, an electron-blocking layer, a light-emitting layer, a hole-blocking layer, an electron transport layer, or an electron injection layer in accordance with their functions. The organic compound layer is mainly composed of an organic compound, and may contain inorganic atoms and an inorganic compound. For example, the organic compound layer may contain, for example, copper, lithium, magnesium, aluminum, iridium, platinum, molybdenum, or zinc. The organic compound layer may be disposed between the first electrode and the second electrode, and may be disposed in contact with the first electrode and the second electrode.
The organic compound layer, such as the hole injection layer, the hole transport layer, the electron-blocking layer, the light-emitting layer, the hole-blocking layer, the electron transport layer, or the electron injection layer, included in the organic light-emitting device according to an embodiment of the present disclosure is formed by a method described below.
For the organic compound layer included in the organic light-emitting device according to an embodiment of the present disclosure, a dry process, such as a vacuum evaporation method, an ionized evaporation method, sputtering, or plasma, may be employed. Alternatively, instead of the dry process, it is also possible to employ a wet process in which a material is dissolved in an appropriate solvent and then a film is formed by a known coating method, such as spin coating, dipping, a casting method, a Langmuir-Blodgett (LB) technique, or an ink jet method.
When the layer is formed by, for example, the vacuum evaporation method or the solution coating method, crystallization and so forth are less likely to occur, and good stability with time is obtained. In the case of forming a film by the coating method, the film may be formed in combination with an appropriate binder resin.
Non-limiting examples of the binder resin include poly(vinyl carbazole) resins, polycarbonate resins, polyester resins, acrylonitrile butadiene styrene (ABS) resins, acrylic resins, polyimide resins, phenolic resins, epoxy resins, silicone resins, and urea resins.
These binder resins may be used alone as a homopolymer or copolymer or in combination as a mixture of two or more. Furthermore, additives, such as a known plasticizer, antioxidant, and ultraviolet absorber, may be used, as needed.
A protective layer may be disposed on the second electrode. For example, a glass member provided with a moisture absorbent can be bonded to the second electrode to reduce the entry of, for example, water into the organic compound layer, thereby reducing the occurrence of display defects. In another embodiment, a passivation film composed of, for example, silicon nitride may be disposed on the second electrode to reduce the entry of, for example, water into the organic compound layer. For example, after the formation of the second electrode, the substrate may be transported to another chamber without breaking the vacuum, and a silicon nitride film having a thickness of 2 m may be formed by a chemical vapor deposition (CVD) method to provide a protective layer. After the film deposition by the CVD method, a protective layer may be formed by an atomic layer deposition (ALD) method. Non-limiting examples of the material of the layer formed by the ALD method may include silicon nitride, silicon oxide, and aluminum oxide. Silicon nitride may be deposited by the CVD method on the layer formed by the ALD method. The film formed by the ALD method may have a smaller thickness than the film formed by the CVD method. Specifically, the thickness may be 50% or less, even 10% or less.
A color filter may be disposed on the protective layer. For example, a color filter may be disposed on another substrate in consideration of the size of the organic light-emitting device and bonded to the substrate provided with the organic light-emitting device. A color filter may be formed by patterning on the protective layer using photolithography. The color filter may be composed of a polymer.
A planarization layer may be disposed between the color filter and the protective layer. The planarization layer is provided for the purpose of reducing the unevenness of the layer underneath. The planarization layer may be referred to as a “material resin layer” without limiting its purpose. The planarization layer may be composed of an organic compound. A low- or high-molecular-weight organic compound may be used. A high-molecular-weight organic compound can be used.
The planarization layers may be disposed above and below (or on) the color filter and may be composed of the same or different component materials. Specific examples thereof include poly(vinyl carbazole) resins, polycarbonate resins, polyester resins, acrylonitrile butadiene styrene (ABS) resins, acrylic resins, polyimide resins, phenolic resins, epoxy resins, silicone resins, and urea resins.
The organic light-emitting device or an organic light-emitting apparatus may include an optical component, such as a microlens, on the outgoing light side. The microlens can be composed of, for example, an acrylic resin or an epoxy resin. The microlens may be used to increase the amount of light emitted from the organic light-emitting device or the organic light-emitting apparatus and to control the direction of the light emitted. The microlens may have a hemispherical shape. In the case of a hemispherical shape, among tangents to the hemisphere, there is a tangent parallel to the insulating layer. The point of contact of the tangent with the hemisphere is the vertex of the microlens. The vertex of the microlens can be determined in the same way for any cross-sectional view. That is, among the tangents to the semicircle of the microlens in the cross-sectional view, there is a tangent parallel to the insulating layer, and the point of contact of the tangent with the semicircle is the vertex of the microlens.
The midpoint of the microlens can be defined. In the cross section of the microlens, when a segment is hypothetically drawn from the point where an arc shape ends to the point where another arc shape ends, the midpoint of the segment can be referred to as the midpoint of the microlens. The cross section to determine the vertex and midpoint may be a cross section perpendicular to the insulating layer.
An opposite substrate may be disposed on the planarization layer. The opposite substrate is disposed at a position corresponding to the substrate described above and thus is called an opposite substrate. The opposite substrate may be composed of the same material as the substrate described above. When the above-described substrate is referred to as a first substrate, the opposite substrate may be referred to as a second substrate.
An organic light-emitting apparatus including organic light-emitting devices may include pixel circuits coupled to the organic light-emitting devices. Each of the pixel circuits may be of an active matrix type, which independently controls the emission of first and second light-emitting devices. The active matrix type circuit may be voltage programming or current programming. A driving circuit includes the pixel circuit for each pixel. The pixel circuit may include a light-emitting device, a transistor to control the luminance of the light-emitting device, a transistor to control the timing of the light emission, a capacitor to retain the gate voltage of the transistor to control the luminance, and a transistor to connect to GND without using the light-emitting device.
The light-emitting apparatus includes a display area and a peripheral area disposed around the display area. The display area includes a pixel circuit, and the peripheral area includes a display control circuit. The mobility of a transistor contained in the pixel circuit may be lower than the mobility of a transistor contained in the display control circuit.
The gradient of the current-voltage characteristics of the transistor contained in the pixel circuit may be smaller than the gradient of the current-voltage characteristic of the transistor contained in the display control circuit. The gradient of the current-voltage characteristics can be measured by what is called Vg-Ig characteristics. The transistor contained in the pixel circuit is a transistor coupled to a light-emitting device, such as a first light-emitting device.
An organic light-emitting apparatus including an organic light-emitting device may include multiple pixels. Each pixel includes subpixels configured to emit colors different from each other. The subpixels may have respective red, green, and blue (RGB) emission colors.
Light emerges from a region of the pixel, also called a pixel aperture. This region is the same as a first region. The pixel aperture may be 15 μm or less, and may be m or more. More specifically, the pixel aperture may be, for example, 11 μm, 9.5 μm, 7.4 μm, or 6.4 μm. The distance between subpixels may be 10 μm. Specifically, the distance may be 8 μm, 7.4 μm, or 6.4 μm.
The pixels may be arranged in a known pattern in plan view. For example, a stripe pattern, a delta pattern, a Pen Tile matrix pattern, or the Bayer pattern may be used. The shape of each subpixel in plan view may be any known shape. Examples of the shape of the subpixel include quadrilaterals, such as rectangles and rhombi, and hexagons. Of course, if the shape is close to a rectangle, rather than an exact shape, it is included in the rectangle. The shape of the subpixel and the pixel arrangement can be used in combination.
The organic light-emitting device according to an embodiment can be used as a component member of a display apparatus or lighting apparatus. Other applications include exposure light sources for electrophotographic image-forming apparatuses, backlights for liquid crystal displays, and light-emitting apparatuses including white-light sources and color filters.
The display apparatus may be an image information-processing unit having an image input unit that receives image information from an area or linear CCD sensor, a memory card, or any other source, an information-processing unit that processes the input information, and a display unit that displays the input image. The display apparatus includes multiple pixels, and at least one of the multiple pixels may include the organic light-emitting device according to the present embodiment and a transistor coupled to the organic light-emitting device.
The display unit of an image pickup apparatus or an inkjet printer may have a touch panel function. The driving mode of the touch panel function may be, but is not particularly limited to, an infrared mode, an electrostatic capacitance mode, a resistive film mode, or an electromagnetic inductive mode. The display apparatus may also be used for a display unit of a multifunction printer.
The following describes a display apparatus according to the present embodiment with reference to the attached drawings.
The transistors and capacitive elements may be disposed under or in the interlayer insulating layer 1.
Each transistor may be electrically coupled to a corresponding one of the first electrodes 2 through a contact hole (not illustrated).
The insulating layer 3 is also called a bank or pixel separation film. The insulating layer 3 covers the edge of each first electrode 2 and surrounds the first electrode 2. Portions that are not covered with the insulating layer 3 are in contact with the organic compound layer 4 and serve as light-emitting regions.
The organic compound layer 4 includes a hole injection layer 41, a hole transport layer 42, a first light-emitting layer 43, a second light-emitting layer 44, and an electron transport layer 45.
The second electrode 5 may be a transparent electrode, a reflective electrode, or a semi-transparent electrode.
The protective layer 6 reduces the penetration of moisture into the organic compound layer 4. Although the protective layer 6 is illustrated as a single layer, the protective layer 6 may include multiple layers, and each layer may be an inorganic compound layer or an organic compound layer.
The color filter 7 is separated into 7R, 7G, and 7B according to its color. The color filter 7 may be disposed on a planarization film (not illustrated). A resin protective layer (not illustrated) may be disposed on the color filter 7. The color filter 7 may be disposed on the protective layer 6. Alternatively, the color filter 7 may be disposed on an opposite substrate, such as a glass substrate, and then bonded.
A display apparatus 100 illustrated in
The mode of electrical connection between the electrodes (anode 21 and cathode 23) included in each organic light-emitting device 26 and the electrodes (source electrode 17 and drain electrode 16) included in a corresponding one of the TFTs 18 is not limited to the mode illustrated in
In the display apparatus 100 illustrated in
In the display apparatus 100 illustrated in
The transistors used in the display apparatus 100 illustrated in
The transistors in the display apparatus 100 illustrated in
In the organic light-emitting device according to the present embodiment, the luminance is controlled by the TFT devices, which are an example of switching devices; thus, an image can be displayed at respective luminance levels by arranging multiple organic light-emitting devices in the plane. The switching devices according to the present embodiment are not limited to the TFT devices and may be low-temperature polysilicon transistors or active-matrix drivers formed on a substrate such as a Si substrate. The expression “on a substrate” can also be said to be “in the substrate”. Whether transistors are formed in the substrate or TFT devices are used is selected in accordance with the size of a display unit. For example, in the case where the display unit has a size of about 0.5 inches, organic light-emitting devices can be disposed on a Si substrate.
The display apparatus according to the present embodiment may include a color filter having red, green, and blue portions. In the color filter, the red, green, and blue portions may be arranged in a delta arrangement.
The display apparatus according to the present embodiment may be used for the display unit of a portable terminal. In that case, the display apparatus may have both a display function and an operation function. Examples of the portable terminal include mobile phones such as smartphones, tablets, and head-mounted displays.
The display apparatus according to the present embodiment may be used for a display unit of an image pickup apparatus including an optical unit including multiple lenses and an image pickup device that receives light passing through the optical unit. The image pickup apparatus may include a display unit that displays information acquired by the image pickup device. The display unit may be a display unit exposed to the outside of the image pickup apparatus or a display unit disposed in a finder. The image pickup apparatus may be a digital camera or a digital camcorder.
The timing suitable for imaging is only for a short time; thus, the information may be displayed as soon as possible. The display apparatus including the organic light-emitting device can be used more suitably than liquid crystal displays because the organic light-emitting device has a fast response time. The display apparatus including the organic light-emitting device can be used more suitably than liquid crystal displays for such apparatuses required to have a high display speed.
The image pickup apparatus 1100 includes an optical unit (not illustrated). The optical unit includes multiple lenses and is configured to form an image on an image pickup device in the housing 1104. The relative positions of the multiple lenses can be adjusted to adjust the focal point. This operation can also be performed automatically. The image pickup apparatus may translate to a photoelectric conversion apparatus. Examples of an image capturing method employed in the photoelectric conversion apparatus may include a method for detecting a difference from the previous image and a method of cutting out an image from images always recorded, instead of sequentially capturing images.
The lighting apparatus is, for example, an apparatus that lights a room. The lighting apparatus may emit light of white, neutral white, or any color from blue to red. A light control circuit that controls the light may be provided.
The lighting apparatus may include the organic light-emitting device according to the present embodiment and a power supply circuit coupled thereto. The power supply circuit is a circuit that converts an AC voltage into a DC voltage. The color temperature of white is 4,200 K, and the color temperature of neutral white is 5,000 K. The lighting apparatus may include a color filter.
The lighting apparatus according to the present embodiment may include a heat dissipation unit. The heat dissipation unit is configured to release heat in the device to the outside of the device and is composed of, for example, a metal having a high specific heat and liquid silicone.
The tail lamp 1501 may include an organic light-emitting device according to the present embodiment. The tail lamp 1501 may include a protective member that protects the organic light-emitting device. The protective member may be composed of any transparent material having high strength to some extent and can be composed of, for example, polycarbonate. The polycarbonate may be mixed with, for example, a furandicarboxylic acid derivative or an acrylonitrile derivative.
The automobile 1500 may include an automobile body 1503 and windows 1502 attached thereto. The windows 1502 may be transparent displays if the windows are not used to check the front and back of the automobile. The transparent displays may include an organic light-emitting device according to the present embodiment.
In this case, the components, such as the electrodes, of the organic light-emitting device are formed of transparent members.
The moving object according to the present embodiment may be, for example, a ship, an aircraft, or a drone. The moving object may include a body and a lighting unit attached to the body. The lighting unit may emit light to indicate the position of the body. The lighting unit includes the organic light-emitting device according to the present embodiment.
Examples of applications of the display apparatuses of the above embodiments will be described with reference to
The glasses 1600 further include a control unit 1603. The control unit 1603 functions as a power source that supplies electric power to the image pickup apparatus 1602 and the display apparatus. The control unit 1603 controls the operation of the image pickup apparatus 1602 and the display apparatus. The lens 1601 has an optical system for focusing light on the image pickup apparatus 1602.
The control unit 1612 may include a gaze detection unit that detects the gaze of a wearer. Infrared light may be used for gaze detection. An infrared light-emitting unit emits infrared light to an eyeball of a user who is gazing at a displayed image. An image of the eyeball is captured by detecting the reflected infrared light from the eyeball with an image pickup unit having light-receiving elements. The deterioration of image quality is reduced by providing a reduction unit that reduces light from the infrared light-emitting unit to the display unit when viewed in plan. The user's gaze at the displayed image is detected from the image of the eyeball captured with the infrared light. Any known method can be employed to the gaze detection using the captured image of the eyeball. As an example, a gaze detection method based on a Purkinje image of the reflection of irradiation light on a cornea can be employed. More specifically, the gaze detection process is based on a pupil-corneal reflection method. Using the pupil-corneal reflection method, the user's gaze is detected by calculating a gaze vector representing the direction (rotation angle) of the eyeball based on the image of the pupil and the Purkinje image contained in the captured image of the eyeball.
A display apparatus according to an embodiment of the present disclosure may include an image pickup apparatus including light-receiving elements, and may control an image displayed on the display apparatus based on the gaze information of the user from the image pickup apparatus. Specifically, in the display apparatus, a first field of view at which the user gazes and a second field of view other than the first field of view are determined on the basis of the gaze information. The first field of view and the second field of view may be determined by the control unit of the display apparatus or may be determined by receiving those determined by an external control unit. In the display area of the display apparatus, the display resolution of the first field of view may be controlled to be higher than the display resolution of the second field of view. That is, the resolution of the second field of view may be lower than that of the first field of view.
The display area includes a first display area and a second display area different from the first display area. Based on the gaze information, an area of higher priority is determined from the first display area and the second display area. The first display area and the second display area may be determined by the control unit of the display apparatus or may be determined by receiving those determined by an external control unit. The resolution of an area of higher priority may be controlled to be higher than the resolution of an area other than the area of higher priority. In other words, the resolution of an area of a relatively low priority may be low.
Artificial intelligence (AI) may be used to determine the first field of view or the high-priority area. The AI may be a model configured to estimate the angle of gaze from the image of the eyeball and the distance to a target object located in the gaze direction, using the image of the eyeball and the actual direction of gaze of the eyeball in the image as teaching data. The AI program may be stored in the display apparatus, the image pickup apparatus, or an external apparatus. When the AI program is stored in the external apparatus, the AI program is transmitted to the display apparatus via communications.
In the case of controlling the display based on visual detection, smart glasses that further include an image pickup apparatus that captures an external image can be used. The smart glasses can display the captured external information in real time.
The second row has the light-emitting portions 36 at positions corresponding to the positions between the light-emitting portions 36 in the first row. In other words, the multiple light-emitting portions 36 are also spaced apart in the column direction. The arrangement in
As described above, the use of an apparatus including the organic light-emitting device according to the present embodiment enables a stable display with good image quality even for a long time.
While the present disclosure will be described below by examples, the present disclosure is not limited to these examples.
Exemplified compound C-1 was synthesized according to the following scheme.
The following reagents and solvents were placed in a 200-mL recovery flask.
Compound f-1: 6.08 g (20.0 mmol)
Compound f-2: 2.27 g (20.0 mmol)
Sodium carbonate: 5.3 g (50.0 mmol)
Pd(PPh3)4: 578 mg
The reaction solution was heated and stirred at 60° C. for 5 hours under a stream of nitrogen. After the completion of the reaction, the mixture was extracted with toluene, and then the organic layer was concentrated to dryness. The resulting solid was purified by silica gel column chromatography (toluene-ethyl acetate mixture) to give 3.0 g (yield: 58%) of f-3 as a transparent solid.
The following reagent and solvents were placed in a 50-mL recovery flask.
Compound f-4: 3.10 g (20.0 mmol)
Iridium chloride hydrate: 1.60 g
The reaction solution was heated and stirred at 130° C. for 5 hours under a stream of nitrogen. After the completion of the reaction, the reaction solution was filtered, and the resulting solid was washed on the filter with water and methanol to give 3.4 g (yield: 63%) of a yellow solid (f-5).
The following reagents and solvents were placed in a 100-mL recovery flask.
Compound f-5: 1.07 g (1.00 mmol)
Silver triflate: 0.514 g (2.00 mmol)
Methylene chloride: 30 mL
The reaction solution was stirred at room temperature for 7 hours under a stream of nitrogen. After the completion of the reaction, the solvents were removed from the reaction solution at 40° C. to give 1.56 g of a yellowish brow solid (f-6).
The following reagents and solvent were placed in a 100-mL recovery flask.
Compound f-3: 2.55 g (1.00 mmol)
The reaction solution was heated and stirred at 90° C. for 5 hours under a stream of nitrogen. After the completion of the reaction, the reaction solution was filtered, and the resulting solid was washed on the filter with water and methanol. The resulting solid was purified by silica gel column chromatography (toluene-ethyl acetate mixture) to give 0.17 g (yield: 23%) of a yellow solid (exemplified compound C-1).
Exemplified compound C-1 was subjected to mass spectrometry with MALDI-TOF-MS (Bruker Autoflex LRF).
Measured value: m/z=755
Calculated value: C41H28IrN3=755
As presented in Tables 5 to 7, exemplified compounds of Examples 2 to 24 were synthesized as in Example 1, except that raw material f-1 of Example 1 was changed to raw material 1, raw material f-2 to raw material 2, and raw material f-4 to raw material 3. The resulting exemplified compounds were subjected to mass spectrometry as in Example 1. The measured values (m/z) are presented.
Exemplified compound A-16 was synthesized according to the following scheme.
The following reagents and solvents were placed in a 100-mL recovery flask.
Compound f-3: 5.10 g (20.0 mmol)
Iridium chloride hydrate: 1.60 g
The reaction solution was heated and stirred at 130° C. for 5 hours under a stream of nitrogen. After the completion of the reaction, the reaction solution was filtered, and the resulting solid was washed on the filter with water and methanol to give 4.3 g (yield: 58%) of a yellow solid (f-7).
The following reagents and solvents were placed in a 100-mL recovery flask.
Compound f-7: 1.47 g (1.00 mmol)
Compound f-8: 0.40 g (4.00 mmol)
Sodium carbonate: 1.06 g (10.0 mmol)
The reaction solution was heated and stirred at 100° C. for 6 hours under a stream of nitrogen. After cooling, methanol was added thereto. The mixture was filtered and then washed with methanol to give 0.42 g (yield: 52%) of a yellow solid (exemplified compound A-16).
Exemplified compound A-16 was subjected to mass spectrometry with MALDI-TOF-MS (Bruker Autoflex LRF).
Measured value: m/z=800
Calculated value: C43H32IrO2N3=800
As presented in Table 8, exemplified compounds of Examples 26 to 30 were synthesized as in Example 25, except that raw material f-3 of Example 25 was changed to raw material 1 and raw material f-8 to raw material 2. The resulting exemplified compounds were subjected to mass spectrometry as in Example 25. The measured values (m/z) are presented.
Exemplified compound E-1 was synthesized according to the following scheme.
The following reagents and solvent were placed in a 100-mL recovery flask.
Compound A-16: 0.80 g (1.00 mmol)
Compound f-3: 0.64 g (2.50 mmol)
Sodium carbonate: 1.06 g (10.0 mmol)
The reaction solution was subjected to degassing with nitrogen and then heated and stirred at 180° C. for 6 hours. After cooling, methanol was added thereto. The mixture was filtered and then washed with methanol. The resulting solid was purified by silica gel column chromatography (toluene-ethyl acetate mixture) to give 0.14 g (yield: 15%) of a yellow solid (exemplified compound E-1).
Exemplified compound E-1 was subjected to mass spectrometry with MALDI-TOF-MS (Bruker Autoflex LRF).
Measured value: m/z=955
Calculated value: C57H36IrN3=955
As presented in Table 9, exemplified compounds of Examples 32 and 33 were synthesized as in Example 31, except that raw material A-16 of Example 31 was changed to raw material 1 and raw material f-3 to raw material 2. The resulting exemplified compounds were subjected to mass spectrometry as in Example 31. The measured values (m/z) are presented.
An organic light-emitting device having a bottom-emission structure was produced in which an anode, a hole injection layer, a hole transport layer, an electron-blocking layer, a light-emitting layer, a hole-blocking layer, an electron transport layer, an electron injection layer, and a cathode were sequentially formed on a substrate.
An ITO film was formed on a glass substrate and subjected to desired patterning to form an ITO electrode (anode). The ITO electrode had a thickness of 100 nm. The substrate on which the ITO electrode had been formed in this way was used as an ITO substrate in the following steps. Next, vapor deposition was performed by resistance heating in a vacuum chamber at 1.33×10−4 Pa to continuously form organic compound layers and an electrode layer presented in Table 10 on the ITO substrate. Here, the opposing electrode (metal electrode layer, cathode) had an electrode area of 3 mm2.
The characteristics of the resulting device were measured and evaluated. As presented in Table 11, the light-emitting device had a maximum emission wavelength of 529 nm and an efficiency of 57 cd/A. The device was subjected to a continuous operation test at a current density of 50 mA/cm2. The time when the percentage of luminance degradation reached 5% was measured.
With regard to measurement instruments, in the Examples, the current-voltage characteristics were measured with a Hewlett-Packard 4140B microammeter, and the luminance was measured with a Topcon BM7.
The LUMO levels of the host materials and the assist materials are described in parentheses in Table 11. Each of the LUMO levels is calculated as follows: The ionization potential (IP) is determined with an AC-3 photoelectron spectrometer in air, available from Riken Keiki Co., Ltd. The LUMO level is calculated by subtracting the optical band gap (BG) determined with a UV-visible spectrophotometer, available from JASCO Corporation, from the resulting ionization potential.
Organic light-emitting devices in Examples 35 to 41 were produced in the same manner as in Example 34, except that the materials of the light-emitting layers were appropriately changed to materials presented in Table 11. The resulting devices were evaluated in the same manner as in Example 34. The time when the percentage of luminance degradation reaches 5% is indicated by the ratio when the time in Example 34 is 1.0. Table 11 presents the measurement results. The LUMO levels of the host materials and the assist materials calculated in the same manner as in Example 34 are indicated in the parentheses in Table 11.
In Table 11, each of the dopant materials of Examples 34 to 36 is a compound represented by formula [1], where Rn is a tertiary alkyl group having 4 or more carbon atoms. Thus, the emission wavelength is 529 nm to 530 nm, which is the optimal emission wavelength as green. In Table 11, each of the dopant materials of Examples 37 to 40 is a compound represented by formula [2], where R31 is a tertiary alkyl group having 4 or more carbon atoms. Thus, the emission wavelength is longer than those of the dopant materials of Examples 34 to 36. The dopant material in Example 41 is a compound represented by formula [2], where R31 is not a tertiary alkyl group having 4 or more carbon atoms. Thus, the emission wavelength is even longer. In addition, the devices in Examples 34 to 40 have low luminance degradation. This is presumably due to a small influence of decomposition during vapor deposition.
An organic light-emitting device in Example 34 was produced in the same manner as in Example 34, except that the materials and thicknesses were changed to those presented in Table 12. The characteristics of the resulting device were measured and evaluated in the same way as in Example 34.
The characteristics of the resulting device were measured and evaluated in the same way as in Example 34. As presented in Table 13, the light-emitting device had a maximum emission wavelength of 530 nm and an efficiency of 56 cd/A. The LUMO levels of the host materials and the assist materials calculated in the same manner as in Example 34 are indicated in the parentheses in Table 13.
Organic light-emitting devices in Examples 43 to 48 and Comparative examples 1 to 4 were produced in the same manner as in Example 42, except that the materials of the light-emitting layers were appropriately changed to materials presented in Table 13. Compounds Q-2-1 and S-4-1 are illustrated below.
The resulting devices were evaluated in the same manner as in Example 42. The time when the percentage of luminance degradation reaches 5% is indicated by the ratio when the time in Example 42 is 1.0. Table 13 presents the measurement results.
The LUMO levels of the host materials and the assist materials calculated in the same manner as in Example 42 are indicated in the parentheses in Table 13.
From Table 13, the host materials used in Comparative examples 1 to 4 contain a nitrogen atom, an oxygen atom, and/or a sulfur atom, and the resulting devices have lower efficiency and shorter life than the devices in Examples 42 to 48 in which the host materials are hydrocarbons.
The devices in Examples 42 to 46 contain the assist materials having lower LUMO levels than the respective host materials. Thus, the devices have higher efficiency than the devices in Example 47, in which no assist material is contained, and in Example 48, in which the assist material having a higher LUMO level than the host material is contained. From this, by selecting a hydrocarbon as the host material and an assist material having a lower LUMO level than the host material, it is possible to provide a device having high efficiency and long life.
The organic light-emitting device according to an embodiment of the present disclosure emits light having superior color purity as green and has high luminous efficiency and superior driving durability characteristics.
The organic compound according to an embodiment of the present disclosure emits light suitable for green light emission and has high chemical stability. Thus, the use of the organic compound according to an embodiment of the present disclosure as the component material of the organic light-emitting device enables the organic light-emitting device to have superior light-emitting characteristics and superior durability characteristics.
While the present disclosure has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
This application claims the benefit of Japanese Patent Application No. 2021-119628 filed Jul. 20, 2021, which is hereby incorporated by reference herein in its entirety.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-119628 | Jul 2021 | JP | national |
