Patent Application
20240023438
This application claims priority under 35 U.S.C. § 119 to Korean Patent Application No. 10-2022-0085268, filed on Jul. 11, 2022, in the Korean Intellectual Property Office, the disclosure of which is incorporated by reference herein in its entirety.
The disclosure relates to a condensed cyclic compound, an organic light-emitting device including the same, and an electronic apparatus including the organic light-emitting device.
Organic light-emitting devices are self-emissive devices, which have improved characteristics in terms of viewing angles, response time, brightness, driving voltage, and response speed, and produce full-color images.
An organic light-emitting device may include an anode, a cathode, and an organic layer arranged between the anode and the cathode and including an emission layer. A hole transport region may be between the anode and the emission layer, and an electron transport region may be between the emission layer and the cathode. Holes provided from the anode may move toward the emission layer through the hole transport region, and electrons provided from the cathode may move toward the emission layer through the electron transport region. The holes and the electrons recombine in the emission layer to produce excitons. The excitons may transition from an excited state to a ground state, thus generating light.
Provided are a condensed cyclic compound, an organic light-emitting device employing the same, and an electronic apparatus including the organic light-emitting device.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to an aspect of the disclosure, provided is a condensed cyclic compound represented by Formula 1:
In Formula 1,
In Formula 2,
According to another aspect of the disclosure, an organic light-emitting device includes a first electrode, a second electrode, and an organic layer arranged between the first electrode and the second electrode and including an emission layer, wherein the organic layer includes at least one condensed cyclic compound represented by Formula 1.
The condensed cyclic compound may be included in the emission layer of the organic layer, and the condensed cyclic compound included in the emission layer may act as a dopant.
According to another aspect of the disclosure, an electronic apparatus includes the organic light-emitting device.
The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with
The FIGURE is a schematic cross-sectional view of an organic light-emitting device according to an exemplary embodiment.
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the FIGURES, to explain aspects. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present
It will be understood that, although the terms “first,” “second,” “third” etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, “a first element,” “component,” “region,” “layer” or “section” discussed below could be termed a second element, component, region, layer or section without departing from the teachings herein.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, “a,” “an,” “the,” and “at least one” do not denote a limitation of quantity, and are intended to cover both the singular and plural, unless the context clearly indicates otherwise. For example, “an element” has the same meaning as “at least one element,” unless the context clearly indicates otherwise.
“Or” means “and/or.” As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
Furthermore, relative terms, such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the FIGURES. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the FIGURES. For example, if the device in one of the FIGURES is turned over, elements described as being on the “lower” side of other elements would then be oriented on “upper” sides of the other elements. The exemplary term “lower,” can therefore, encompasses both an orientation of “lower” and “upper,” depending on the particular orientation of the FIGURE. Similarly, if the device in one of the FIGURES is turned over, elements described as “below” or “beneath” other elements would then be oriented “above” the other elements. The exemplary terms “below” or “beneath” can, therefore, encompass both an orientation of above and below.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10% or 5% of the stated value.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
According to an embodiment, a condensed cyclic compound represented by Formula 1 may be provided:
In Formula 1,
In Formula 2,
In Formula 1 and Formula 2,
In the condensed cyclic compound according to an embodiment, Y1 may be B.
In the condensed cyclic compound according to an embodiment,
In the condensed cyclic compound according to an embodiment, CY1 to CY4 may each independently be a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, a thiophene group, a furan group, an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group.
In the condensed cyclic compound according to an embodiment, CY1 to CY4 may each independently be a benzene group, a naphthalene group, or a pyridine group.
In the condensed cyclic compound according to an embodiment,
In the condensed cyclic compound according to an embodiment,
In the condensed cyclic compound according to an embodiment, in Formula 1, a1 to a3 may each be 1.
In the condensed cyclic compound according to an embodiment, CY5 and CY6 may each independently be a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, a thiophene group, a furan group, an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an iso-oxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group.
In the condensed cyclic compound according to an embodiment, CY5 and CY6 may each independently be a benzene group, a naphthalene group, or a pyridine group. In some embodiments, CY5 and CY6 may each be a benzene group.
In the condensed cyclic compound according to an embodiment, T1 to T3 may each independently be represented by one of Formulae 2-1 to 2-12:
In Formulae 2-1 to 2-12, descriptions on R5 and R6 may be the same as the descriptions on R5 and R6 in Formula 2.
In the condensed cyclic compound according to an embodiment, in Formula 2,
In the condensed cyclic compound according to an embodiment, R1 to R3, R5, and R6 may each independently be:
In the condensed cyclic compound according to an embodiment,
In Formulae 9-1 to 9-61, 9-201 to 9-237, 10-1 to 10-129, and 10-201 to 10-350, * indicates a binding site to a neighboring atom, Ph is a phenyl group, TMS is a trimethylsilyl group, and TMG is a trimethylgermyl group.
In the condensed cyclic compound according to an embodiment, b4 may be 2, each R4 each independently be one of Formulae 9-1 to 9-39.
The condensed cyclic compound according to an embodiment may be any one of Compounds 1 to 103:
According to another aspect of the disclosure, an organic light-emitting device may include: a first electrode; a second electrode; and an organic layer arranged between the first electrode and the second electrode and including an emission layer, wherein the organic layer may include at least one condensed cyclic compound according to an embodiment.
In light-emitting device according to an embodiment, the condensed cyclic compound may be included in the emission layer.
In the light-emitting device according to an embodiment, the emission layer may further include a host, and a content of the host may be greater than a content of the condensed cyclic compound.
In the light-emitting device according to an embodiment, the emission layer may emit fluorescence.
In the light-emitting device according to an embodiment, the condensed cyclic compound may emit fluorescence.
In the light-emitting device according to another embodiment, the emission layer may further include a phosphorescent dopant, and a content of the phosphorescent dopant may be less than a content of the condensed cyclic compound.
In the light-emitting device according to another embodiment, the emission layer may emit phosphorescence, or phosphorescence and fluorescence.
In the light-emitting device according to an embodiment, the emission layer may emit blue light having a maximum emission wavelength of 400 nm to 490 nm.
In the light-emitting device according to an embodiment,
According to another aspect of the disclosure, an electronic apparatus may include the organic light-emitting device according to an embodiment.
The condensed cyclic compound according to the disclosure may satisfy the structure of Formula 1, and include Core A described below. As Moiety A is essentially included in Core A, the condensed cyclic compound represented by Formula 1 may have a high oscillator strength, and Dexter energy transfer may be inhibited:
In Moiety A, * and *′ may each indicate a binding site to a neighboring atom.
In addition, (X1)n1 in Core A may have a structure different from that of Moiety A. As a result, Core A may have an asymmetric structure. As Core A has an asymmetric structure, the condensed cyclic compound represented by Formula 1 may have a higher oscillator strength and the Dexter energy transfer may be further inhibited.
As such, the condensed cyclic compound represented by Formula 1 may provide an improved thermal stability as well as improved solubility, and decomposition of the condensed cyclic compound represented by Formula 1 may be inhibited.
Moreover, by including Core A, the condensed cyclic compound represented by Formula 1 may have a high S1 energy level and the highest occupied molecular orbital (HOMO) energy level. As such, the condensed cyclic compound represented by Formula 1 may emit deep blue light.
For example, the condensed cyclic compound represented by Formula 1 may include three or more substituents represented by Formula 2 (e.g., carbazole). As a result, the condensed cyclic compound represented by Formula 1 may have a S1 energy level greater than or equal to 3.0 eV, and a HOMO energy level less than or equal to −5.0 eV. According to this, the condensed cyclic compound represented by Formula 1 may stably emit deep blue light.
Therefore, the electronic apparatus using the condensed cyclic compound represented by Formula 1, for example, the organic light-emitting device may have characteristics of excellent color quality, low driving voltage, high efficiency, and long lifespan.
The HOMO energy level, lowest unoccupied molecular orbital (LUMO) energy level, energy gap, S1 energy level, and T1 energy level of some of the condensed cyclic compounds represented by Formula 1 were evaluated by using Gaussian 09 that performs molecular structure optimizations according to density functional theory (DFT) at a degree of B3LYP. The results thereof are shown in Table 1.
From Table 1, it is confirmed that the condensed cyclic compound represented by Formula 1 has characteristics that are suitable for use as a host of an electronic apparatus, for example, an organic light-emitting device.
According to an embodiment, a maximum emission wavelength (also referred to as an emission peak wavelength, λmax) of the emission peak of the emission spectrum or the electroluminescence spectrum of the condensed cyclic compound represented by Formula 1 may be in a range of about 400 nm to about 490 nm.
The synthesis method of the condensed cyclic compound represented by Formula 1 may be recognized by those skilled in the art by referring to Synthesis Examples to be described later.
The condensed cyclic compound represented by Formula 1 may be suitable to be used as a dopant of the organic layer of the organic light-emitting device, for example, the emission layer of the organic layer, and more specifically, may be suitable to be used as a fluorescent dopant. Thus, according to another aspect of the disclosure, provided is an organic light-emitting device including a first electrode, a second electrode, and an organic layer arranged between the first electrode and the second electrode and including an emission layer, wherein the organic layer includes at least one condensed cyclic compound represented by Formula 1.
The organic light-emitting device may have characteristics of excellent driving voltage, high efficiency, and long lifespan by including the organic layer including the condensed cyclic compound represented by Formula 1.
The condensed cyclic compound represented by Formula 1 may be used in between a pair of electrodes of the organic light-emitting device. For example, the condensed cyclic compound represented by Formula 1 may be included in the emission layer. In this regard, the condensed cyclic compound may act as a dopant, and the emission layer may further include a host (that is, a content of the condensed cyclic compound represented by Formula 1 in the emission layer is greater than a content of the host).
According to an embodiment, the emission layer may emit blue light. For example, the emission layer may emit blue light having a maximum emission wavelength in a range of about 400 nm to about 490 nm.
The expression “(an organic layer) includes at least one of condensed cyclic compounds” used herein may include a case in which “(an organic layer) includes identical condensed cyclic compounds represented by Formula 1” and a case in which “(an organic layer) includes two or more different condensed cyclic compounds represented by Formula 1.”
For example, the organic layer may include, as the condensed cyclic compound, only Compound 1. In this embodiment, Compound 1 may be included in the emission layer of the organic light-emitting device. In one or more embodiments, the organic layer may include, as the condensed-cyclic compound, Compound 1 and Compound 2. In this regard, Compound 1 and Compound 2 may exist in an identical layer (for example, Compound 1 and Compound 2 all may exist in an emission layer).
The first electrode may be an anode, which is a hole injection electrode, and the second electrode may be a cathode, which is an electron injection electrode; or the first electrode may be a cathode, which is an electron injection electrode, and the second electrode may be an anode, which is a hole injection electrode.
In an embodiment, in the organic light-emitting device, the first electrode is an anode, and the second electrode is a cathode, and the organic layer may further include a hole transport region located between the first electrode and the emission layer and an electron transport region located between the emission layer and the second electrode, and the hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, a buffer layer, or a combination thereof, and the electron transport region may include a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
The term “organic layer” used herein refers to a single layer and/or a plurality of layers located between the first electrode and the second electrode of the organic light-emitting device. The “organic layer” may include, in addition to an organic compound, an organometallic complex including metal.
The
A substrate may be additionally disposed under the first electrode 11 or on the second electrode 19. The substrate may be a conventional substrate used in organic light-emitting devices, e.g., a glass substrate or a transparent plastic substrate, each having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water repellency.
The first electrode 11 may be produced by depositing or sputtering, onto the substrate, a material for forming the first electrode 11. The first electrode 11 may be an anode. The material for forming the first electrode 11 may be selected from materials with a high work function for easy hole injection. The first electrode 11 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. The material for forming the first electrode 11 may be indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), or zinc oxide (ZnO). In one or more embodiments, the material for forming the first electrode 11 may be metal, such as magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag).
The first electrode 11 may have a single-layered structure or a multi-layered structure including a plurality of layers. For example, the first electrode 11 may have a three-layered structure of ITO/Ag/ITO, but the structure of the first electrode 11 is not limited thereto.
The organic layer 15 is located on the first electrode 11.
The organic layer 15 may include a hole transport region, an emission layer, and an electron transport region.
The hole transport region may be between the first electrode 11 and the emission layer.
The hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, a buffer layer, or any combination thereof.
The hole transport region may include only either a hole injection layer or a hole transport layer. In one or more embodiments, the hole transport region may have a hole injection layer/hole transport layer structure or a hole injection layer/hole transport layer/electron blocking layer structure, wherein, for each structure, respective layers are sequentially stacked in this stated order from the first electrode 11.
When the hole transport region includes a hole injection layer, the hole injection layer may be formed on the first electrode 11 by using one or more suitable methods, for example, vacuum deposition, spin coating, casting, and/or Langmuir-Blodgett (LB) deposition.
When a hole injection layer is formed by vacuum deposition, the deposition conditions may vary according to a material that is used to form the hole injection layer, and the structure and thermal characteristics of the hole injection layer. For example, the deposition conditions may include a deposition temperature of about 100° C. to about 500° C., a vacuum pressure of about 10−8 torr to about 10−3 torr, and a deposition rate of about 0.01 Å/sec to about 100 Å/sec. However, the deposition conditions are not limited thereto.
When the hole injection layer is formed using spin coating, coating conditions may vary according to the material used to form the hole injection layer, and the structure and thermal properties of the hole injection layer. For example, a coating speed may be from about 2,000 rpm to about 5,000 rpm, and a temperature at which a heat treatment is performed to remove a solvent after coating may be from about 80° C. to about 200° C. However, the coating conditions are not limited thereto.
The conditions for forming the hole transport layer and the electron blocking layer may be the same as the conditions for forming the hole injection layer.
The hole transport region may include at least one of m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, spiro-TPD, spiro-NPB, methylated NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate)(PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), (polyaniline)/poly(4-styrenesulfonate) (PANI/PSS), a compound represented by Formula 201, a compound represented by Formula 202, or a combination thereof:
R101 to R108, R111 to R119 and R121 to R124 in Formulae 201 and 202 may each independently be:
R109 in Formula 201 may be selected from:
According to an embodiment, the compound represented by Formula 201 may be represented by Formula 201A below, but embodiments of the disclosure are not limited thereto:
For example, the compound represented by Formula 201, and the compound represented by Formula 202 may include compounds HT1 to HT20 illustrated below, but are not limited thereto:
A thickness of the hole transport region may be in the range of about 100 Å to about 10,000 Å, for example, about 100 Å to about 1,000 Å. When the hole transport region includes at least one of a hole injection layer and a hole transport layer, a thickness of the hole injection layer may be in a range of about 100 Å to about 10,000 Å, for example, about 100 Å to about 1,000 Å, and a thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å, for example, about 100 Å to about 1,500 Å. When the thicknesses of the hole transport region, the hole injection layer and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.
The hole transport region may further include, in addition to these materials, a charge-generation material for the improvement of conductive properties. The charge-generation material may be homogeneously or non-homogeneously dispersed in the hole transport region.
The charge-generation material may be, for example, a p-dopant. The p-dopant may be a quinone derivative, a metal oxide, or a cyano group-containing compound, but embodiments of the disclosure are not limited thereto. For example, non-limiting examples of the p-dopant are: a quinone derivative, such as tetracyanoquinonedimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ), and F6-TCNQ; a metal oxide, such as a tungsten oxide and a molybdenum oxide; and a cyano group-containing compound, such as Compounds HT-D1 and F12, but are not limited thereto:
The hole transport region may include a buffer layer.
The buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, and thus, efficiency of the light-emitting device may be improved.
Then, an emission layer may be formed on the hole transport region by vacuum deposition, spin coating, casting, LB deposition, or the like. When the emission layer is formed by vacuum deposition or spin coating, the deposition or coating conditions may be similar to those applied in forming the hole injection layer although the deposition or coating conditions may vary according to a material that is used to form the hole transport layer.
Meanwhile, when the hole transport region includes an electron blocking layer, a material for the electron blocking layer may be selected from materials for the hole transport region described above and materials for a host to be explained later. However, the material for the electron blocking layer is not limited thereto. For example, when the hole transport region includes an electron blocking layer, a material for the electron blocking layer may be mCP, which will be explained later.
The emission layer may include a host and a dopant, and the dopant may include the condensed cyclic compound represented by Formula 1.
The emission layer may further include a host in addition to the condensed cyclic compound represented by Formula 1. The host may be one kind of compound, or a mixture of two or more different types of compounds. When the emission layer further includes the host, in the emission layer, the fluorescent compound may act as a fluorescent emitter, and a content of the fluorescent compound may be less than a content of the host.
For example, the host may include a fluorene-containing compound, a carbazole-containing compound, a dibenzofuran-containing compound, a dibenzothiophene-containing compound, an indenocarbazole-containing compound, an indolocarbazole-containing compound, a benzofurocarbazole-containing compound, a benzothienocarbazole-containing compound, an acridine-containing compound, a dihydroacridine-containing compound, a triindolobenzene-containing compound, a pyridine-containing compound, a pyrimidine-containing compound, a triazine-containing compound, a silicon-containing compound, a cyano group-containing compound, a phosphine oxide-containing compound, a sulfoxide-containing compound, a sulfonyl-containing compound, or any combination thereof.
For example, the host may be a compound including at least one carbazole ring and at least one cyano group or a phosphine oxide-containing compound.
The host may include at least one compound selected from, for example, CBP, mCBP (Compound H7) and Compound H1 to H24:
In addition to the condensed cyclic compound represented by Formula 1, the emission layer may further include a phosphorescent dopant. When the emission layer further includes the phosphorescent dopant, the condensed cyclic compound represented by Formula 1 may be employed as the host.
In one or more embodiments, the phosphorescent dopant may include at least one transition metal as a central metal.
The phosphorescent dopant may include a monodentate ligand, a bidentate ligand, a tridentate ligand, a tetradentate ligand, a pentadentate ligand, a hexadentate ligand, or any combination thereof.
The phosphorescent dopant may be electrically neutral.
For example, the phosphorescent dopant may include an organometallic compound represented by Formula 51 below:
In Formula 51,
In an embodiment, M in Formula 51 may be Pt, Pd, or Au.
In another embodiment, a bond between X51 and M in Formula 51 may be a coordinate bond.
In yet another embodiment, in Formula 51, X51 may be C, and a bond between X11 and M may be a coordinate bond. That is, X51 in Formula 51 may be C in a carbene moiety.
In another embodiment, ring CY51 to ring CY54 in Formula 51 may each independently be i) a first ring, ii) a second ring, iii) a condensed ring in which two or more first rings are condensed with each other, iv) a condensed ring in which two or more second rings are condensed with each other, or v) a condensed ring in which at least one first ring is condensed with at least one second ring,
An amount (weight) of the dopant in the emission layer 15 may be in a range of about 0.1 part by weight to about 20 parts by weight based on 100 parts by weight of the emission layer 15.
When the organic light-emitting device 10 is a full-color organic light-emitting device 10, the emission layer may be patterned into a red emission layer, a green emission layer, and a blue emission layer. In one or more embodiments, due to a stacked structure including a red emission layer, a green emission layer, and/or a blue emission layer, the emission layer may emit white light.
When the emission layer includes a host and a dopant, an amount of the dopant may be in a range of about 0.01 part by weight to about 15 parts by weight based on 100 parts by weight of the host, but embodiments of the disclosure are not limited thereto.
A thickness of the emission layer may be in a range of about 100 Å to about 1,000 Å, for example, about 200 Å to about 600 Å. When the thickness of the emission layer is within these ranges, excellent light-emission characteristics may be obtained without a substantial increase in driving voltage.
An electron transport region may be located on the emission layer.
The electron transport region may include a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
For example, the electron transport region may have a hole blocking layer/electron transport layer/electron injection layer structure or an electron transport layer/electron injection layer structure, and the structure of the electron transport region is not limited thereto. The electron transport layer may have a single-layered structure or a multi-layered structure including two or more different materials.
Conditions for forming the hole blocking layer, the electron transport layer, and the electron injection layer which constitute the electron transport region may be understood by referring to the conditions for forming the hole injection layer.
When the electron transport region includes a hole blocking layer, the hole blocking layer may include, for example, at least one of BCP, Bphen, and BAlq but embodiments of the disclosure are not limited thereto:
A thickness of the hole blocking layer may be in a range of about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å. When the thickness of the hole blocking layer is within these ranges, excellent hole blocking characteristics may be obtained without a substantial increase in driving voltage.
The electron transport layer may further include at least one of BCP, Bphen, Alq3, BAlq, TAZ, NTAZ, or any combination thereof:
In one or more embodiments, the electron transport layer may include at least one of ET1 to ET25, but are not limited thereto:
A thickness of the electron transport layer may be in the range of about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layer is within the range described above, the electron transport layer may have satisfactory electron transporting characteristics without a substantial increase in driving voltage.
The electron transport layer may include a metal-containing material in addition to the material as described above.
The metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (lithium quinolate, LiQ) or ET-D2:
The electron transport region may include an electron injection layer that promotes the flow of electrons from the second electrode 19 thereinto.
The electron injection layer may include LiF, NaCl, CsF, Li2O, BaO, or a combination thereof.
A thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å, and, for example, about 3 Å to about 90 Å. When the thickness of the electron injection layer is within the ranges described above, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 19 is located on the organic layer 15. The second electrode 19 may be a cathode. A material for forming the second electrode 19 may be metal, an alloy, an electrically conductive compound, or a combination thereof, which have a relatively low work function. For example, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag) may be used as the material for forming the second electrode 19. In one or more embodiments, to manufacture a top-emission type light-emitting device, a transmissive electrode formed using ITO or IZO may be used as the second electrode 19.
Hereinbefore, the organic light-emitting device has been described with reference to the FIGURE, but embodiments of the disclosure are not limited thereto.
According to another aspect of the disclosure, a diagnostic composition may include at least one condensed cyclic compound represented by Formula 1.
The condensed cyclic compound represented by Formula 1 provides high luminescence efficiency, and accordingly, the diagnostic composition including the condensed cyclic compound may have high diagnostic efficiency.
The diagnostic composition may be used in various applications including a diagnosis kit, a diagnosis reagent, a biosensor, and a biomarker.
The term “C1-C60 alkyl group” as used herein refers to a linear or branched saturated aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms, and non-limiting examples thereof include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, and a hexyl group. The term “C1-C60 alkylene group” as used herein refers to a divalent group having the same structure as the C1-C60 alkyl group.
The term “C1-C60 alkoxy group” used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and examples thereof include a methoxy group, an ethoxy group, and an isopropoxy group.
The term “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethynyl group and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkynyl group.
The term “C3-C10 cycloalkyl group” as used herein refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The term “C3-C10 cycloalkylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkyl group.
The term “C1-C10 heterocycloalkyl group” as used herein refers to a monovalent monocyclic group having at least one heteroatom of N, O, P, Si, S, B, Se, Ge, or any combination thereof, as a ring-forming atom and 1 to 10 carbon atoms, and examples thereof include a tetrahydrofuranyl group and a tetrahydrothiophenyl group. The term “C1-C10 heterocycloalkylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkyl group.
The term “C3-C10 cycloalkenyl group” as used herein refers to a monovalent monocyclic group that has 3 to 10 carbon atoms and at least one carbon-carbon double bond in the ring thereof and no aromaticity, and non-limiting examples thereof include a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. The term “C3-C10 cycloalkenylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkenyl group.
The term “C1-C10 heterocycloalkenyl group” as used herein refers to a monovalent monocyclic group that has at least one heteroatom of N, O, P, Si, S, B, Se, Ge, or any combination thereof as a ring-forming atom, 1 to 10 carbon atoms, and at least one carbon-carbon double bond in its ring. Examples of the C1-C10 heterocycloalkenyl group are a 2,3-dihydrofuranyl group, and a 2,3-dihydrothiophenyl group. The term “C1-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms, and the term “C6-C60 arylene group” as used herein refers to a divalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms. Examples of the C6-C60 aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a chrysenyl group. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be fused to each other. The C7-C60 alkylaryl group refers to a C6-C60 aryl group substituted with at least one C1-C60 alkyl group.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system that has at least one heteroatom of N, O, P, Si, S, B, Se, Ge, or any combination thereof as a ring-forming atom, and 1 to 60 carbon atoms. The term “C1-C60 heteroarylene group” as used herein refers to a divalent group having a carbocyclic aromatic system that has at least one heteroatom of N, O, P, S, B, Se, Ge, or any combination thereof as a ring-forming atom, and 1 to 60 carbon atoms. Examples of the C1-C60 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, and an isoquinolinyl group. When the C6-C60 heteroaryl group and the C6-C60 heteroarylene group each include two or more rings, the rings may be fused to each other. The C2-C60 alkylheteroaryl group refers to a C1-C60 heteroaryl group substituted with at least one C1-C60 alkyl group.
The term “C6-C60 aryloxy group” as used herein indicates —OA102 (wherein A102 is a C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein indicates —SA103 (wherein A103 is a C6-C60 aryl group).
The term “C1-C60 heteroaryloxy group” as used herein refers to —OA104 (wherein A104 is the C1-C60 heteroaryl group), and the term “C1-C60 heteroarylthio group” as used herein refers to —SA105 (wherein A105 is the C1-C60 heteroaryl group).
The term “monovalent non-aromatic condensed polycyclic group” as used herein refers to a monovalent group (for example, having 8 to 60 carbon atoms) having two or more rings condensed to each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed polycyclic group include a fluorenyl group. The term “divalent non-aromatic condensed polycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed polycyclic group described above.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein refers to a monovalent group (for example, having 2 to 60 carbon atoms) having two or more rings condensed with each other, a heteroatom of N, O, P, Si, S, B, Se, Ge, or any combination thereof, other than carbon atoms, as a ring-forming atom, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed heteropolycyclic group include a carbazolyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed heteropolycyclic group described above.
The term “C6-C30 carbocyclic group” as used herein refers to a saturated or unsaturated cyclic group having, as a ring-forming atom, 5 to 30 carbon atoms only. The C6-C30 carbocyclic group may be a monocyclic group or a polycyclic group.
The term “C1-C30 heterocyclic group” as used herein refers to a saturated or unsaturated cyclic group having, as a ring-forming atom, at least one heteroatom of N, O, Si, P, S, B, Se, Ge, or any combination thereof other than 1 to 30 carbon atoms. The C1-C30 heterocyclic group may be a monocyclic group or a polycyclic group.
As used herein, the number of carbons in each group that is substituted (e.g., C1-C60) excludes the number of carbons in the substituent. For example, a C1-C60 alkyl group can be substituted with a C1-C60 alkyl group. The total number of carbons included in the C1-C60 alkyl group substituted with the C1-C60 alkyl group is not limited to 60 carbons. In addition, more than one C1-C60 alkyl substituent may be present on the C1-C60 alkyl group. This definition is not limited to the C1-C60 alkyl group and applies to all substituted groups that recite a carbon range.
At least one substituent of the substituted C6-C30 carbocyclic group, the substituted C1-C30 heterocyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C7-C60 alkylaryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted C2-C60 alkyl heteroaryl group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be:
Hereinafter, a compound and an organic light-emitting device according to embodiments are described in detail with reference to Synthesis Example and Examples. However, the organic light-emitting device is not limited thereto. The wording “B was used instead of A” used in describing Synthesis Examples means that an amount of A used was identical to an amount of B used, in terms of a molar equivalent.
1) Synthesis of Compound 1-1
9-(3,4,5-trichlorophenyl)-9H-carbazole (3.37 g, 9.72 mmol), Compound 1-2 (11.728 g, 20.42 mmol), Pd2(dba)3 (0.89 g, 0.97 mmol), Sphos (0.798 g, 1.94 mmol), and NaOBu-t (3.27 g, 34.03 mmol) were added into 300 ml of xylene under nitrogen and refluxed for 30 minutes. Then, the reaction was terminated by using an ammonium chloride solution. An extraction process was performed thereon by using ethyl acetate. MgSO4 was added for drying, and the solvent was removed. Then, a purification process was performed by column chromatography using MC:Hexane (1:3) to obtain 10 g of white solid. (yield: 74%)
LCMS (m/z) calculated: 1391.43 g/mol, found: [M+] 1389.829 g/mol
2) Synthesis of Compound 1
Compound 1-1 (5 g, 3.6 mmol) was dissolved in 90 ml of t-butylbenzene under nitrogen, and then cooled down to −78° C. After t-BuLi (6.2 ml, 8.99 mmol) was added thereto, the temperature was raised to 60° C., followed by stirring for 1 hour and 30 minutes. After cooling to 0° C., boron tribromide (0.69 ml, 7.20 mmol) was added, followed by stirring for 1 hour and 30 minutes at room temperature. After cooling to 0° C., N,N-diisopropylethyl acetate (1.22 ml, 7.20 mmol) was added thereto, and a heating process was performed thereon at 120° C. for 4 hours. The reaction was terminated by using a sodium acetate solution (1.0 M). After the organic layer was extracted and dried using MgSO4, the solvent was removed, and 1 g of Compound 1 was obtained as a solid through purification by performing column chromatography using MC:Hexane (1:4). (yield: 25%)
LCMS (m/z) calculated: 1364.77 g/mol, found: [M+] 1363.854 g/mol
1) Synthesis of Compound 2′-2
9-(3,4,5-trichlorophenyl)-9H-carbazole (6.0 g, 17.31 mmol), Compound 2′-3 (8.13 g, 17.31 mmol), Pd(dba)2 (0.99 g, 1.73 mmol), Sphos (1.42 g, 3.46 mmol), and NaOBu-t (3.33 g, 34.63 mmol) were added into 350 ml of xylene under nitrogen and refluxed for 30 minutes. Then, the reaction was terminated by using an ammonium chloride solution. An extraction process was performed thereon by using ethyl acetate. MgSO4 was added for drying, and the solvent was removed. Then, a purification process was performed by column chromatography using MC:Hexane (1:3) to obtain 11 g of white solid. (yield: 81%)
LCMS (m/z) calculated: 779.83 g/mol, found: [M+] 778.382 g/mol
2) Synthesis of Compound 2′-1
Compound 2′-2 (5.0 g, 6.41 mmol), 3,5-di-tert-butyl-N-(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)aniline (3.58 g, 6.41 mmol), Pd2(dba)3 (0.59 g, 0.64 mmol), Sphos (1.23 g, 12.82 mmol), and NaOBu-t (1.23 g, 12.82 mmol) were added into 130 ml of xylene and refluxed for 30 minutes. Then the reaction was terminated by the addition of an ammonium chloride solution. An extraction process was performed thereon by using ethyl acetate. MgSO4 was added for drying, and the solvent was removed. Then, a purification process was performed by column chromatography using MC:Hexane (1:3) to obtain 5.2 g of white solid. (yield: 62%)
LCMS (m/z) calculated: 1302.33 g/mol, found: [M+] 1300.803 g/mol
3) Synthesis of Compound 2′
Compound 2′-1 (5.3 g, 4.07 mmol) was dissolved in 100 ml of t-butylbenzene under nitrogen, and then cooled down to −78° C. After t-BuLi (7.01 ml, 10.17 mmol) was added thereto, the temperature was raised to 60° C., followed by stirring for 1 hour and 30 minutes. After cooling to 0° C., boron tribromide (0.78 ml, 8.14 mmol) was added, followed by stirring for 1 hour and 30 minutes at room temperature. After cooling to 0° C., N,N-diisopropylethyl acetate (1.38 ml, 8.14 mmol) was added thereto, and a heating process was performed thereon at 120° C. for 4 hours. The reaction was terminated by using a sodium acetate solution (1.0 M). After the organic layer was extracted and dried using MgSO4, the solvent was removed, and 0.8 g of Compound 2′ was obtained as a solid through purification by performing column chromatography using MC:Hexane (1:4). (yield: 17%)
LCMS (m/z) calculated: 1275.67 g/mol, found: [M+] 1274.828 g/mol
1) Synthesis of Compound 3′-1
1-bromo-2,3-dichlorobenzene (1.25 g, 5.53 mmol), Compound 3′-2 (6.80 g, 12.17 mmol), Pd2(dba)3 (0.51 g, 0.55 mmol), Sphos (0.45 g, 1.11 mmol), and NaOBu-t (1.86 g, 19.37 mmol) were added into 110 ml of xylene and refluxed for 30 minutes. The reaction was terminated by using an ammonium chloride solution. An extraction process was performed thereon by using ethyl acetate. MgSO4 was added for drying, and the solvent was removed. Then, a purification process was performed by column chromatography using MC:Hexane (1:3) to obtain 4.3 g of white solid. (yield: 63%)
LCMS (m/z) calculated: 1226.23 g/mol, found: [M+] 1224.771 g/mol
2) Synthesis of Compound 3′
Compound 3′-1 (4.3 g, 3.51 mmol) was dissolved in 87 ml of t-butylbenzene under nitrogen, and then cooled down to −78° C. After t-BuLi (6.1 ml, 8.77 mmol) was added thereto, the temperature was raised to 60° C., followed by stirring for 1 hour and 30 minutes. After cooling to 0° C., boron tribromide (0.68 ml, 7.01 mmol) was added, followed by stirring for 1 hour and 30 minutes at room temperature. After cooling to 0° C., N,N-diisopropylethyl acetate (1.19 ml, 7.01 mmol) was added thereto, and a heating process was performed thereon at 120° C. for 4 hours. The reaction was terminated by using a sodium acetate solution (1.0 M). After the organic layer was extracted and dried using MgSO4, the solvent was removed, and 0.6 g of Compound 3′ was obtained as a solid through purification by performing column chromatography using MC:Hexane (1:4). (yield: 13%)
LCMS (m/z) calculated: 1199.58 g/mol, found: [M+] 1198.796 g/mol
An ITO glass substrate was cut to a size of 50 mm×50 mm×0.5 mm and then, sonicated in acetone isopropyl alcohol and pure water, each for 15 minutes, and then, cleaned by exposure to ultraviolet (UV) light ozone for 30 minutes.
Then, HAT-CN was deposited on the ITO electrode (anode) on the glass substrate to form a hole injection layer having a thickness of 100 Å, NPB was deposited on the hole injection layer to form a first hole transport layer having a thickness of 500 Å, TCTA was deposited on the first hole transport layer to form a second hole transport layer having a thickness of 50 Å and mCP was deposited on the second hole transport layer to form an electron blocking layer having a thickness of 50 Å.
A first host (H1), a second host (H2), and an emitter (Compound 1) were co-deposited on the electron blocking layer to form an emission layer having a thickness of 400 Å. In this regard, the first host and the second host were mixed in a ratio of 60:40, and the emitter was adjusted to be 3 wt % based on the total weight of the first host, the second host, and the emitter.
DBFPO was deposited on the emission layer to form a hole blocking layer having a thickness of 100 Å, and then DBFPO and Liq were co-deposited thereon at a weight ratio of 5:5 to form an electron transport layer having a thickness of 300 Å, and then, Liq was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and Al was deposited on the electron injection layer to form a cathode having a thickness of 1,000 Å, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in the same manner as in Example 1, except that compounds shown in Table 2 were each used instead of Compound 1 in forming an emission layer.
Evaluation Example 1: Characterization of organic light-emitting device
The T95 lifespan characteristic, which is time taken for initial luminance to decrease down by 95% (at 1,200 cd/m2, hr), luminescence efficiency, driving voltage (V), and maximum emission wavelength (nm) of the organic light-emitting device manufactured according to Example 1 and Comparative Examples 1 to 4 were measured and evaluated by using a current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A). The results are shown in Table 2.
The structures of compounds used in each Comparative Example are as follows:
According to Table 2, compared to the organic light-emitting device of Comparative Examples 1 to 4, the organic light-emitting device of Example 1, which includes Compound 1 in the emission layer, may provide improved luminescence efficiency and lifespan. More specifically, i) when the emitter does not include a moiety represented by Formula 2 as in the organic light-emitting device of Comparative Examples 1 and 2, shortening of lifespan of the organic light-emitting device was observed. In addition, ii) when the emitter includes less than three moieties represented by Formula 2 as in the organic light-emitting device of Comparative Examples 3 and 4, shortening of lifespan (Comparative Example 3) or decline of luminescence efficiency (Comparative Example 4) was observed.
According to the one or more embodiments, as a condensed cyclic compound has characteristics of excellent thermal stability and charge mobility, an electronic apparatus, for example, an organic light-emitting device, employing the condensed cyclic compound may have characteristics of low driving voltage, high efficiency, and long lifespan. Accordingly, by using the condensed cyclic compound, a high-quality organic light-emitting device may be implemented.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0085268 | Jul 2022 | KR | national |
